Organic small molecule semiconducting chromophores for use in organic electronic devices

ABSTRACT

Small organic molecule semi-conducting chromophores containing a pyridalthiadiazole, pyridaloxadiazole, or pyridaltriazole core structure are disclosed. Such compounds can be used in organic heterojunction devices, such as organic small molecule solar cells and transistors.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application is a continuation of U.S. application Ser. No.13/988,756, which is a National Phase application under 35 USC § 371 ofInternational Application No. PCT/US2011/061963 having an InternationalFiling Date of Nov. 22, 2011, which claims priority benefit of U.S.Provisional Patent Application No. 61/416,251, filed Nov. 22, 2010. Theentire contents of that application is those applications are herebyincorporated by reference herein.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with United Stated government support undergrant no. DE-DC0001009 awarded by the Center for Energy EfficientMaterials of the Department of Energy and under grant no.N-00014-04-0411 awarded by the Office of Naval Research. The governmenthas certain rights in the invention.

BACKGROUND OF THE INVENTION

Solution-processed organic photovoltaic devices (OPV) have emerged as apromising energy technology due to their ease of processing, low-cost,and ability to be fabricated, onto light-weight flexible substrates.Polymer based OPV's have by far been the most studied, and powerconversion efficiencies (PCE's) above 6% have recently been reported forpolymer:full creme, bulk heterojunction (BHJ) devices. On the otherhand, solution processed small molecule BHJ devices have received farless attention. Such molecular hetero junctions (MHJ) have severaladvantages over their polymer counterparts, in that small molecules havewell defined structures, are easily functionatized, are mono-disperse,are readily purified, and do not suffer from batch-to-batch variations.Reports of efficient solution processed MHJ devices have recentlyemerged that have utilized merocyanine dyes, squaraine dyes, isoindigo,and diketopyrrolopyrrole based chromophores as the light harvestingdonor component with a fullerene acceptor. PCE's have reached upwards of4% for such devices. While these results are encouraging, there stillexits a need for the development of novel discrete light harvestingmaterials. Key parameters for effective small molecule donors includehaving broad and efficient optical absorption that extends into thenear-IR region to maximize photon absorption, deep HOMO levels from −5to −5.5 eV to maximize open circuit voltages, relatively planarstructures for high charge carrier mobility, high solution viscosity andsolubilizing side chains for solution to film processing. Additionally,it is important that novel structures have facile and highly tunablesyntheses to enable rapid and cheap generation of molecular libraries.

The present invention seeks to address the need for improved lightharvesting molecules for molecular heterojunction devices by providingnovel and advantageous materials for use in such devices.

SUMMARY OF THE INVENTION

In one embodiment, the present invention is directed to organicnon-polymeric semiconducting chromophores containing thepyridalthiadiazole (PT, [1,2,5]thiadiazolo[3,4-c]pyridine),pyridaloxadiazole (PO, [1,2,5]oxadiazolo[3,4-c]pyridine), orpyridaltriazole (P3N, 2-H-[1,2,3]triazolo[4,5-c]pyridine) (or a2-substituted P3N derivative) organic structure for use inheterojunction devices, such as organic small molecule solar cells andtransistors. In one embodiment, the present invention is directed tonon-polymeric electron-donating and electron-accepting chromophoreshaving a pyridalthiadiazole (PT, [1,2,5]thiadiazolo[3,4-c]pyridine),pyridaloxadiazole (PO, [1,2,5]oxadiazolo[3,4-c]pyridine), orpyridaltriazole (P3N, 2-H-[1,2,3]triazolo[4,5-c]pyridine) (or a2-substituted P3N derivative) core structure. In another embodiment, thepresent invention is directed to optoelectronic devices comprising anactive layer composition of a mixture of a non-polymericlight-harvesting electron-donating chromophore based on a PT, PO, or P3Ncore structure with an electron-accepting material, such as a fullerene,methanofullerene, rylene diimides or related π-conjugated organicelectron acceptors. Organic or inorganic electron acceptors can be used.In another embodiment, the present invention is directed tooptoelectronic devices comprising an active layer composition of amixture of a non-polymeric light-harvesting electron-acceptingchromophore, based on a PT, PO, or P3N core structure with anelectron-donating material. Organic or inorganic electron donors can beused. The present invention is also directed to methods of fabricatingthe devices by solution processing. In one embodiment, all active layersof the described optoelectronic devices are formed from solutionscomprising of non-polymeric discrete organic materials.

In one embodiment, the invention embraces compounds of Formula I:

and, in additional embodiments, compounds of Formula Ia, Formula Ib, andFormula Ic:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ isCH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁,X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, andwhen X₂ is CH, Y₂ is N;

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

A₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of such groups include, but are not limitedto, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, di thienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each B₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of such groups include, but are not limitedto, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

Each B₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups.

In another embodiment, the invention embraces compounds of Formula II:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ isCH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁,X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, andwhen X₂ is CH, Y₂ is N;

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer between 0 and 5, inclusive;

A₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of such groups include, but are not limitedto, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each B₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of such groups include, but are not limitedto, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each B₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups.

In one embodiment, n is an integer between 0 and 5, inclusive. Inanother embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5.

In some embodiments of Formula II, X₁ and X₂ are each N and Y₁ and Y₂are each CH. In some embodiments of Formula II, X₁ and X₂ are each CHand Y₁ and Y₂ are each N.

In some embodiments of Formula II, X₁ and X₂ are each N, Y₁ and Y₂ areeach CH and each M is S. In some embodiments of Formula II, X₁ and X₂are each CH, Y₁ and Y₂ are each N, and each M is S.

In some embodiments of Formula II, X₁ and X₂ are each N, Y₁ and Y₂ areeach CH and each M is O. In some embodiments of Formula II, X₁ and X₂are each CH, Y₁ and Y₂ are each N, and each M is O.

In preferred embodiments, B₂ is selected from the group consisting of anonentity, H, F, a C₁-C₁₆ alkyl group, thiophene, benzothiophene,benzofuran, and benzothiazole.

In further embodiments, B₂ is phenyl, substituted at the p-position withdiphenylamine (i.e., the B₂ moiety is triphenylamine)

In another embodiment, the invention embraces compounds of Formula II ofFormula IIa, Formula IIb, or Formula IIc:

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer between and 5, inclusive;

A₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of such groups include, but are not limitedto, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′-RR′-cyclopeta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each B₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of such groups include, but are not limitedto, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each B₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups.

In one embodiment, n is an integer between 0 and 5, inclusive. Inanother embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5.

In some embodiments of Formula IIa, each M is S.

In some embodiments of Formula IIa, each M is O.

In some embodiments of Formula IIb, each M is S.

In some embodiments of Formula IIb, each M is O.

In some embodiments of Formula IIc, each M is S.

In some embodiments of Formula IIc, each M is O.

In some embodiments, the compounds of Formula II are selected fromcompounds of Formula IId:

where Q₁ is C or Si;

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ isCH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁,X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, andwhen X₂ is CH, Y₂ is N;

n is 0, 1, 2, or 3;

R₇ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, benzofuran-2-yl,benzothiophene-2-yl, and benzothiazole-2-yl; and

R₈ is selected from H, C₁-C₁₆ alkyl or —O—C₁-C₁₆ alkyl.

In one embodiment of Formula IId, Q₁ is C.

In one embodiment of Formula IId, Q₁ is Si.

In one embodiment of Formula IId, X₁ and X₂ are N and Y₁ and Y₂ are CH.

In one embodiment of Formula IId, X₁ and X₂ are CH and Y₁ and Y₂ are N.

In one embodiment of Formula IId, n is 2.

In one embodiment of Formula IId, R₇ is selected from H or C₁-C₁₆ alkyl.

In one embodiment of Formula IId, R₇ is selected from benzofuran-2-yl.

In one embodiment of Formula IId, R₇ is selected frombenzothiophene-2-yl.

In one embodiment of Formula IId, R₇ is selected frombenzothiazole-2-yl.

In one embodiment of Formula IId, R₈ is selected from H or C₁-C₁₆ alkyl.

In one embodiment of Formula IId, R₈ is selected from C₁-C₁₆ alkyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, and Y₁ andY₂ are CH.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, and Y₁ andY₂ are N.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, and Y₁ andY₂ are CH.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, and Y₁ andY₂ are N.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are Y₁ d Y₂ are CH,and n is 1.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are N, and n is 1.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂are CH, and n is 1.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are N, and n is 1.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂are CH, n is 1, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 1, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂are CH, n is 1, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 1, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂are CH, n is 1, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 1, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂are CH, n is 1, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 1, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂are CH, and n is 2.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are N, and n is 2.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂are CH, and n is 2.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are N, and n is 2.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂are CH, n is 2, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 2, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂are CH, n is 2, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 2, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂are CH, n is 2, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 2, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂are CH, n is 2, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 2, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, is Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂are CH, and n is 3.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are N, and n is 3.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂are CH, and n is 3.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are N, and n is 3.

In one embodiment of Formula IId, Q₁ is C. X₁ and X₂ are N, Y₁ and Y₂are CH, n is 3, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 3, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂are CH, n is 3, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 3, and R₇ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂are CH, n is 3, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 3, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂are CH, n is 3, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 3, and R₈ is 2-ethyl-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are N, Y₁ and Y₂are CH, n is 3, and R₈ is n-hexyl.

In one embodiment of Formula IId, Q₁ is C, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 3, and R₈ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are N, Y₁ and Y₂are CH, n is 3, and R₈ is n-hexyl.

In one embodiment of Formula IId, Q₁ is Si, X₁ and X₂ are CH, Y₁ and Y₂are N, n is 3, and R₈ is n-hexyl.

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In one embodiment of Formula IId, the compound is of the formula:

In some embodiments of Formula II the compounds are of Formula IIe:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ isCH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁,X₂ and Y₂, are selected from N and CH, where when X₂ is N, Y₂ is CH, andwhen X₂ is CH, Y₂ is N;

n is 0, 1, 2, or 3;

R₇ is selected from II, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, benzofuran-2-yl,benzothiophene-2-yl, benzothiazole-2-yl,4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl, 4,4-bis(C₁-C₁₆alkyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl, and4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene-2-yl; and

R₉ is selected from H, C₁-C₁₆ alkyl or —O—C₁-C₁₆ alkyl.

In one embodiment of Formula IIe, n is 0.

In one embodiment of Formula IIe, n is 1.

In one embodiment of Formula IIe, n is 2.

In one embodiment of Formula IIe, n is 3.

In one embodiment of Formula IIe, X₁ and X₂ are N and Y₁ and Y₂ are CH.

In one embodiment of Formula IIe, X₁ and X₂ are CH and Y₁ and Y₂ are N.

In one embodiment of Formula IIe, R₉ is —O—C₁-C₁₆ alkyl.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉).

In one embodiment of Formula IIe, R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉) and R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl.

In one embodiment of Formula IIe, R₉ is —O—C₁-C₁₆ alkyl and n is 0.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉) and n is 0.

In one embodiment of Formula IIe, R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl and nis 0.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl and nis 0.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl, X₁and X₂ are N, and Y₁ and Y₂ are CH.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl, X₁and X₂ are CH, and Y₁ and Y₂ are N.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl, X₁and X₂ are N, Y₁ and Y₂ are CH, and n is 0.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ is4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene-2-yl, X₁and X₂ are CH, Y₁ and Y₂ are N, and n is 0.

In one embodiment of Formula IIe, R₇ is n-hexyl.

In one embodiment of Formula IIe, R₉ is —O—C₁-C₁₆ alkyl and n is 1.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉) and n is 1.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉) and R₇ isn-hexyl.

In one embodiment of Formula IIe, R₇ is n-hexyl and n is 1.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ isn-hexyl and n is 1.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ isn-hexyl, X₁ and X₂ are N, and Y₁ and Y₂ are CH.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ isn-hexyl, X₁ and X₂ are CH, and Y₁ and Y₂ are N.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ isn-hexyl, X₁ and X₂ are N, Y₁ and Y₂ are CH, and n is 1.

In one embodiment of Formula IIe, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉), R₇ isn-hexyl, X₁ and X₂ are CH, Y₁ and Y₂ are N, and n is 1.

In some embodiments, the compounds of Formula II embrace compounds ofFormula IIf:

where R₉ is H, C₁-C₁₆ alkyl or —O—C₁-C₁₆ alkyl.

In one embodiment of Formula IIf, R₉ is —O—CH₂CH(C₂H₅)(C₄H₉).

In one embodiment of Formula IIf, R₉ is —O—(CH₂)₅CH₃.

In another embodiment, the invention embraces compounds of Formula III:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

where H₁ is selected from A₁, —B₁—B₂, -A₁-B₁—B₂, or

n is an integer between 0 and 5, inclusive;

A₁ (when present) is independently selected from substituted orunsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of such groupsinclude, but are not limited to, thiophene, pyrrole, furan, phenyl,phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, toluene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each B₁ (when present) is independently selected from substituted orunsubstituted aryl or heteroaryl groups such as C₆-C₃₀ substituted orunsubstituted, aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of such groupsinclude, but are not limited to, thiophene, pyrrole, furan, phenyl,phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazolebenzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each B₂ (when present) is independently selected from a nonentity, H, F,a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl orheteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups.

In one embodiment, n is an integer between 0 and 5, inclusive. Inanother embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5.

In another embodiment, the invention embraces compounds of Formula IIIof Formula IIIa, Formula IIIb, Formula IIIc, and Formula IIId:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer between 0 and 5, inclusive;

A₁ (when present) is independently selected from substituted orunsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀) substituted orunsubstituted aryl or heteroaryl groups. Examples of such groupsinclude, but are not limited to, thiophene, pyrrole, furan, phenyl,phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where Rand R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each B₁ (when present) is independently selected from substituted orunsubstituted aryl or heteroaryl groups such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of such groupsinclude, but are not limited to, thiophene, pyrrole, furan, phenyl,phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each B₂ (when present) is independently selected from a nonentity, H, F,a C₁-C₁₆ alkyl group, or a substituted or unsubstituted aryl orheteroaryl group, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups.

In one embodiment, n is an integer between 0 and 5, inclusive. Inanother embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5.

In another embodiment, the invention embraces compounds of Formula IV-V:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ isCH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁,X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, andwhen X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂, and Y₂,X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, andwhen X₃ is CH, Y₃ is N;

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

K₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each E₁ is independently either absent, or selected from substituted orunsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of aryl and heteroarylgroups include, but are not limited to, thiophene, pyrrole, furan,phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene,bithiophene, terthiophene, thienothiophene, dithienothiophene,benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of aryland heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole.

In one embodiment of Formula IV-V, each M is S. In one embodiment ofFormula IV-V, each D₁ is the same moiety. In one embodiment of FormulaIV-V, each D₂ is the same moiety. In one embodiment of Formula IV-V,each D₁ is the same moiety, and each D₂ is the same moiety(independently of D₁). In one embodiment of Formula IV-V, each M is S,each D₁ is the same moiety, and each D₂ is the same moiety(independently of D₁).

In some embodiments of Formula IV-V, X₁, X₂, and X₃ are each N and Y₁,Y₂, and Y₃, are each CH. In some embodiments of Formula IV-V, X₁, X₂,and X₃ are each CH and Y₁, Y₂, and Y₃ are each N.

In some embodiments of Formula IV-V, X₁, X₂, and X₃ are each N and Y₁,Y₂, and Y₃, are each CH, and each M is S. In some embodiments of FormulaIV-V, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N, and eachM is S.

In some embodiments of Formula IV-V, X₁, X₂, and X₃ are each N and Y₁,Y₂, and Y₃, are each CH, and each M is O. In some embodiments of FormulaIV-V, X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N, and eachM is O.

In another embodiment, the invention embraces compounds of Formula IV-Vof Formula IV:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ isCH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁,X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, andwhen X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂, and Y₂,X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, andwhen X₃ is CH, Y₃ is N;

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

K₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazolebenzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole; and

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of aryland heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole.

In one embodiment of Formula IV, each M is S. In one embodiment ofFormula IV, each D₁ is the same moiety. In one embodiment of Formula IV,each D₂ is the same moiety. In one embodiment of Formula IV, each D₁ isthe same moiety, and each D₂ is the same moiety (independently of D₁).In one embodiment of Formula IV, each M is S, each D₁ is the samemoiety, and each D₂ is the same moiety (independently of D₁).

In some embodiments of Formula IV, X₁, X₂, and X₃ are each N and Y₁, Y₂,and Y₃, are each CH. In some embodiments of Formula IV, X₁, X₂, and X₃are each CH and Y₁, Y₂, and Y₃ are each N.

In some embodiments of Formula IV, X₁, X₂, and X₃ are each N and Y₁, Y₂,and Y₃, are each CH, and each M is S. In some embodiments of Formula IV,X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N, and each M isS.

In some embodiments of Formula IV, X₁, X₂, and X₃ are each N and Y₁, Y₂,and Y₃ are each CH, and each M is O. In some embodiments of Formula IV,X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N, and each M isO.

In another embodiment, the invention embraces compounds of Formula IV ofFormula IVa or Formula IVb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

K₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, di thienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole; and

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of aryland heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole.

In one embodiment of Formula IVa, each M is S. In one embodiment ofFormula IVa, each D₁ is the same moiety. In one embodiment of FormulaIVa, each D₂ is the same moiety. In one embodiment of Formula IVa, eachD₁ is the same moiety, and each D₂ is the same moiety (independently ofD₁). In one embodiment of Formula IVa, each M is S, each D₁ is the samemoiety, and each D₂ is the same moiety (independently of D₁).

In one embodiment of Formula IVa, each M is O. In one embodiment ofFormula IVa, each D₁ is the same moiety. In one embodiment of FormulaIVa, each D₂ is the same moiety. In one embodiment of Formula IVa, eachD₁ is the same moiety, and each D2 is the same moiety (independently ofD₁). In one embodiment of Formula IVa, each M is O, each D₁ is the samemoiety, and each D₂ is the same moiety (independently of D₁).

In one embodiment of Formula IVb, each M is S. In one embodiment ofFormula IVb, each D₁ is the same moiety. In one embodiment of FormulaIVb, each D₂ is the same moiety. In one embodiment of Formula IVb, eachD₁ is the same moiety, and each D₂ is the same moiety (independently ofD₁). In one embodiment of Formula IVb, each M is S, each D₁ is the samemoiety, and each D₂ is the same moiety (independently of D₁).

In one embodiment of Formula IVb, each M is O. In one embodiment ofFormula IVb, each D₁ is the same moiety. In one embodiment of FormulaIVb, each D₂ is the same moiety. In one embodiment of Formula IVb, eachD₁ is the same moiety, and each D₂ is the same moiety (independently ofD₁). In one embodiment of Formula IVb, each M is O, each D₁ is the samemoiety, and each D₂ is the same moiety (independently of D₁).

In another embodiment, the invention embraces compounds of Formula IV-Vof Formula V:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ isCH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁,X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, andwhen X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂, and Y₂,X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, andwhen X₃ is CH, Y₃ is N;

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

K₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₁ and E₁ is independently selected from substituted orunsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of aryl and heteroarylgroups include, but are not limited to, thiophene, pyrrole, furan,phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene,bithiophene, terthiophene, thienothiophene, dithienothiophene,benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₉substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of aryland heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole.

In one embodiment of Formula V, each M is S. In one embodiment ofFormula V, each D₁ is the same moiety. In one embodiment of Formula V,each D₂ is the same moiety. In one embodiment of Formula V, each D₁ isthe same moiety, and each D₂ is the same moiety (independently of D₁).In one embodiment of Formula V, each M is S, each D₁ is the same moiety,and each D₂ is the same moiety (independently of D₁).

In some embodiments of Formula V, X₁, X₂, and X₃ are each N and Y₁, Y₂,and Y₃, are each CH. In some embodiments of Formula V, X₁, X₂, and X₃are each CH and Y₁, Y₂, and Y₃ are each N.

In some embodiments of Formula V, X₁, X₂, and X₃ are each N and Y₁, Y₂,and Y₃, are each CH, and each M is S. In some embodiments of Formula V,X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N, and each M isS.

In some embodiments of Formula V, X₁, X₂, and X₃ are each N and Y₁, Y₂,and Y₃, are each CH, and each M is O. In some embodiments of Formula V,X₁, X₂, and X₃ are each CH and Y₁, Y₂, and Y₃ are each N, and each M isO.

In another embodiment, the invention embraces compounds of Formula Va orFormula Vb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

K₁ is independently selected from substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl and heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₁ and E₁ is independently selected from substituted orunsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of aryl and heteroarylgroups include, but are not limited to, thiophene, pyrrole, furan,phenyl, phosphole, benzodithiophene, spirofluorene, spirothiophene,bithiophene, terthiophene, thienothiophene, dithienothiophene,benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole;

each D₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of aryland heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, dithienopyrrole,dithienophosphole, and carbazole.

In one embodiment of Formula Va, each M is S. In one embodiment ofFormula Va, each E₁ is the same moiety. In one embodiment of Formula Va,each D₁ is the same moiety. In one embodiment of Formula Va, each D₂ isthe same moiety. In one embodiment of Formula Va, each E₁ is the samemoiety, each D₁ is the same moiety, and each D₂ is the same moiety(where E₁, D₁, and D₂ are chosen independently of each other). In oneembodiment of Formula Va, each M is S, and each E₁ is the same moiety,each D₁ is the same moiety, and each D₂ is the same moiety (where E₁,D₁, and D₂ are chosen independently of each other).

In one embodiment of Formula Va, each M is O. In one embodiment ofFormula Va, each E₁ is the same moiety. In one embodiment of Formula Va,each D₁ is the same moiety. In one embodiment of Formula Va, each D₂ isthe same moiety. In one embodiment of Formula. Va, each E₁ is the samemoiety, each D₁ is the same moiety, and each D₂ is the same moiety(where E₁, D₁, and D₂ are chosen independently of each other). In oneembodiment of Formula Va, each M is O, and each E₁ is the same moiety,each D₁ is the same moiety, and each D2 is the same moiety (where E₁,D₁, and D₂ are chosen independently of each other).

In one embodiment of Formula Vb, each M is S. In one embodiment ofFormula Vb, each E₁ is the same moiety. In one embodiment of Formula Vb,each D₁ is the same moiety. In one embodiment of Formula Vb, each D₂ isthe same moiety. In one embodiment of Formula Vb, each E₁ is the samemoiety, each D₁ is the same moiety, and each D₂ is the same moiety(where E₁, D₁, and D₂ are chosen independently of each other). In oneembodiment of Formula Vb, each M is S, and each E₁ is the same moiety,each D₁ is the same moiety, and each D₂ is the same moiety (where E₁,D₁, and D₂ are chosen independently of each other).

In one embodiment of Formula Vb, each M is O. In one embodiment ofFormula Vb, each E₁ is the same moiety. In one embodiment of Formula Vb,each D₁ is the same moiety. In one embodiment of Formula Vb, each D₂ isthe same moiety. In one embodiment of Formula Vb, each E₁ is the samemoiety, each D₁ is the same moiety, and each D₂ is the same moiety(where E₁, D₁, and D₂ are chosen independently of each other). In oneembodiment of Formula Vb, each M is O, and each E₁ is the same moiety,each D₁ is the same moiety, and each D₂ is the same moiety (where E₁,D₁, and D₂ are chosen independently of each other).

In another embodiment, the invention embraces compounds of FormulaVI-VII:

where the moiety

is selected from

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ isCH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁,X₂, and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, andwhen X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂, and Y₂,X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, andwhen X₃ is CH, Y₃ is N; and where, independently of X₁, Y₁, X₂, Y₂, X₃,and Y₃, X₄ and Y₄ are selected from N and CH, where when X₄ is N, Y₄ isCH, and when X₄ is CH, Y₄ is N;

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each F₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, toluene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, dithienopyrrole,dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene 2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]dithiophene, where R and R′═C₁-C₃₀ alkylor C₆-C₃₀ aryl;

each G₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole; and

each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of arylor heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VI-VII, each M is S. In other embodimentsof Formula VI-VII, each M is O.

In some embodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each N andY₁, Y₂, Y₃, and Y₄ are each CH. In some embodiments of Formula VI-VII,X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each N.

In some embodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each N andY₁, Y₂, Y₃, and Y₄ are each CH, and each M is S. In some embodiments ofFormula. VI-VII, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄are each N, and each M is S.

In some embodiments of Formula VI-VII, X₁, X₂, X₃, and X₄ are each N andY₁, Y₂, Y₃, and Y₄ are each CH, and each M is O. In some embodiments ofFormula VI-VII, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄are each N, and each M is O.

In some embodiments of Formula VI-VII, each F₁ is the same moiety. Insome embodiments of Formula VI-VII, each G₁ is the same moiety. In someembodiments of Formula VI-VII, each G₂ is the same moiety. In someembodiments of Formula VI-VII, each F₁ is the same moiety, each G₁ isthe same moiety, and each G₂ is the same moiety (where F₁, G₁, and G₂are chosen independently of each other). In some embodiments of FormulaVI-VII, each F₁ is the same moiety, each G₁ is the same moiety, and eachG₂ is the same moiety (where F₁, G₁, and G₂ are chosen independently ofeach other); and M is S. In some embodiments of Formula VI-VII, each F₁is the same moiety, each G₁ is the same moiety, and each G₂ is the samemoiety (where F₁, G₁, and G₂ are chosen independently of each other);and M is O.

In another embodiment, the invention embraces compounds of Formula VI:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ isCH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁,X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, andwhen X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂, and Y₂,X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, andwhen X₃ is CH, Y₃ is N; and where, independently of X₁, Y₁, X₂, Y₂, X₃,and Y₃, X₄ and Y₄ are selected from N and CH, where when is N, Y₄ is CH,and when X₄ is CH, Y₄ is N;

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each F₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, dithienopyrrole,dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b;3,4-b′]-dithiophene, where R and R′═C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each G₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, andcarbazole; and

each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of arylor heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuranisobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VI, each M is S. In other embodiments ofFormula VI, each M is O.

In some embodiments of Formula VI, X₁, X₂, X₃, and X₄ are each N and Y₁,Y₂, Y₃, and Y₄ are each CH. In some embodiments of Formula VI, X₁, X₂,X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each N.

In some embodiments of Formula VI, X₁, X₂, X₃, and X₄ are each N and Y₁,Y₂, Y₃, and Y₄ are each CH, and each M is S. In some embodiments ofFormula VI, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ areeach N, and each M is S.

In some embodiments of Formula VI, X₁, X₂, X₃, and X₄ are each N and Y₁,Y₂, Y₃, and Y₄ are each CH, and each M is O. In some embodiments ofFormula VI, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ areeach N, and each M is O.

In some embodiments of Formula VI, each F₁ is the same. In someembodiments of Formula VI, each G₁ is the same. In some embodiments ofFormula VI, each G₂ is the same. In some embodiments of Formula VI, eachF₁ is the same, each G₁ is the same, and each G₂ is the same (where F₁,B₁, and G₂ are chosen independently of each other). In some embodimentsof Formula VI, each F₁ is the same, each G₁ is the same, and each G₂ isthe same (where F₁, G₁, and G₂ are chosen independently of each other);and M is S. In some embodiments of Formula VI, each F₁ is the same, eachG₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ are chosenindependently of each other); and M is O.

In another embodiment, the invention embraces compounds of Formula VI,such as compounds of Formula VIa or Formula VIb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each F₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, dithienopyrrole,dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene 2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b;3,4-b′]-dithiophene, where R and R′═C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each G₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, (C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, andcarbazole; and

each G₂ is independently selected from a nonentity, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of arylor heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VIa, each M is S. In other embodiments ofFormula VIa, each M is O. In some embodiments of Formula VIa, each F₁ isthe same. In some embodiments of Formula VIa, each G₁ is the same. Insome embodiments of Formula VIa, each G₂ is the same. In someembodiments of Formula VIa, each F₁ is the same, each G₁ is the same,and each G₂ is the same (where F₁, G₁, and G₂ are chosen independentlyof each other). In some embodiments of Formula VIa, each F₁ is the same,each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ arechosen independently of each other); and M is S. In some embodiments ofFormula VIa, each F₁ is the same, each G₁ is the same (where F₁, G₁, andG₂ are chosen independently of each other), and each G₂ is the same; andM is O.

In some embodiments of Formula VIb, each M is S. In other embodiments ofFormula VIb, each M is O. In some embodiments of Formula VIb, each F₁ isthe same. In some embodiments of Formula VIb, each G₁ is the same. Insome embodiments of Formula VIb, each G₂ is the same. In someembodiments of Formula VIb, each F₁ is the same, each G₁ is the same,and each G₂ is the same (where F₁, G₁, and G₂ are chosen independentlyof each other). In some embodiments of Formula VIb, each F₁ is the same,each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ arechosen independently of each other); and M is S. In some embodiments ofFormula VIb, each F₁ is the same, each G₁ is the same (where F₁, G₁, andG₂ are chosen independently of each other), and each G2 is the same; andM is O.

In another embodiment, the invention embraces compounds of Formula VII:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ isCH, and when X₁ is CH, Y₁ is N; and where, independently of X₁ and Y₁,X₂ and Y₂ are selected from N and CH, where when X₂ is N, Y₂ is CH, andwhen X₂ is CH, Y₂ is N; and where, independently of X₁, Y₁, X₂ and Y₂,X₃ and Y₃ are selected from N and CH, where when X₃ is N, Y₃ is CH, andwhen X₃ is CH, Y₃ is N; and where, independently of X₁, Y₁, X₂, Y₂, X₃,and Y₃, X₄ and Y₄ are selected from N and CH, where when X₄ is N, Y₄ isCH, and when X₄ is CH, Y₄ is N;

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each F₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, dithienopyrrole,dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀alkyl or C₆-C₃₀ aryl;

each G₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, andcarbazole; and

each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆;alkyl group, or a substituted or unsubstituted aryl or heteroaryl group,such as C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups,C₆-C₂₀ substituted or unsubstituted aryl or heteroaryl groups, andC₆-C₁₀ substituted or unsubstituted aryl or heteroaryl groups, Examplesof aryl or heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VII, each M is S. In other embodiments ofFormula VII, each M is O.

In some embodiments of Formula VII, X₁, X₂, X₃, and X₄ are each N andY₁, Y₂, Y₃, and Y₄ are each CH. In some embodiments of Formula VII, X₁,X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ are each N.

In some embodiments of Formula VII, X₁, X₂, X₃, and X₄ are each N andY₁, Y₂, Y₃, and Y₄ are each CH, and each M is S. In some embodiments ofFormula VII, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ areeach N, and each M is S.

In some embodiments of Formula VII, X₁, X₂, X₃, and X₄ are each N andY₁, Y₂, Y₃, and Y₄ are each CH, and each M is O. In some embodiments ofFormula VII, X₁, X₂, X₃, and X₄ are each CH and Y₁, Y₂, Y₃, and Y₄ areeach N, and each M is O.

In some embodiments of Formula VII, each F₁ is the same. In someembodiments of Formula VII, each G₁ is the same. In some embodiments ofFormula VII, each G₂, is the same. In some embodiments of Formula VII,each F₁ is the same, each G₁ is the same, and each G₂ is the same (whereF₁, G₁, and G₂ are chosen independently of each other). In someembodiments of Formula VII, each F₁ is the same, each G₁ is the same,and each G₂ is the same (where F₁, G₁, and G₂ are chosen independentlyof each other); and M is S. In some embodiments of Formula VII, each F₁is the same, each G₁ is the same, and each G₂ is the same (where F₁, G₁,and G₂ are chosen independently of each other); and M is O.

In another embodiment, the invention embraces compounds of Formula VII,such as compounds of Formula VIIa or Formula VIIb:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

each F₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, dithienopyrrole,dithienophosphole, and carbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene 2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]dithiophene, where R and R′═C₁-C₃₀ alkylor C₆-C₃₀ aryl.

Each G₁ is independently selected from substituted or unsubstituted arylor heteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted arylor heteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of aryl or heteroaryl groups include, butare not limited to, thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine,imidazole, benzoxazole, benzoxadiazole, benzothiazole, benzimidazole,benzofuran, isobenzofuran, thiadiazole, perfluorylbenzene, andcarbazole.

Each G₂ is independently selected from a nonentity, H, F, a C₁-C₁₆ alkylgroup, or a substituted or unsubstituted aryl or heteroaryl group, suchas C₆-C₃₀ substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of arylor heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some embodiments of Formula VIIa, each M is S. In other embodimentsof Formula VIIa, each M is O. In some embodiments of Formula VIIa, eachF₁ is the same. In some embodiments of Formula VIIa, each G₁ is thesame. In some embodiments of Formula VIIa, each G₂ is the same. In someembodiments of Formula VIIa, each F₁ is the same, each G₁ is the same,and each G₂ is the same (where G₁ and G₂ are chosen independently ofeach other). In some embodiments of Formula VIIa, each F₁ is the same,each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂ arechosen independently of each other); and M is S. In some embodiments ofFormula VIIa, each F₁ is the same, each G₁ is the same (where F₁, G₁,and G₂ are chosen independently of each other), and each G₂ is the same;and M is O.

In some embodiments of Formula VIIb, each M is S. In other embodimentsof Formula VIIb, each M is O. In some embodiments of Formula VIIb, eachF₁ is the same. In some embodiments of Formula VIIb, each G₁ is thesame. In some embodiments of Formula VIIb, each G₂ is the same. In someembodiments of Formula VIIb, each F₁ is the same, each G₁ is the same,and each G₂ is the same (where F₁, G₁, and G₂ are chosen independentlyof each other). In some embodiments of Formula VIIb, each F₁ is thesame, each G₁ is the same, and each G₂ is the same (where F₁, G₁, and G₂are chosen independently of each other); and M is S. In some embodimentsof Formula VIIb, each F₁ is the same, each G₁ is the same, and each G₂is the same (where F₁, G₁, and G₂ are chosen independently of eachother); and M is O.

In additional embodiments, the invention embraces compounds of Formula1-2-3-4-5:

where P₁ is selected from

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer from 0 to 5 inclusive;

R₂ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl,and C₂-C₁₆ alkynyl;

J is selected from CH and N;

X is S, O, or NH when X is CH; and X is S when J is N;

R₄ is selected from aryl or aryl substituted with alkyl, such as C₆-C₃₀aryl optionally substituted with one or more C₁-C₁₆ alkyl groups, C₆-C₂₀aryl optionally substituted with one or more C₁-C₁₆ alkyl groups, andC₆-C₁₀ aryl groups optionally substituted with one or more C₁-C₁₆ alkylgroups, and

where DONOR is as defined below.

In one embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5;

In additional embodiments, the invention embraces compounds of Formula1, Formula 2, Formula 3, Formula 4, or Formula 5:

In the structures for Formula 1, Formula 2, Formula 3, Formula 4, andFormula 5 above:

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer from 0 to 5 inclusive;

R₂ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl,and C₂-C₁₆ alkynyl;

J is selected from CH and N;

X is S, O, or NH when X is CH; and X is S when J is N;

R₄ is selected from aryl or aryl substituted with alkyl, such as C₆-C₃₀aryl optionally substituted with one or more C₁-C₁₆ alkyl groups, C₆-C₂₀aryl optionally substituted with one or more C₁-C₁₆ alkyl groups, andC₆-C₁₀ aryl groups optionally substituted with one or more C₁-C₁₆ alkylgroups, and

where DONOR is as defined below.

In one embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5

In additional embodiments, the invention embraces compounds of Formula6-7-8:

where P₂ is selected from:

where M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer from 0 to 5 inclusive;

R₂ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl,and C₂-C₁₆ alkynyl;

J is selected from CH and N;

X is S, O, or NH when X is CH; and X is S when J is N;

R₆ is selected from aryl, perfluoroaryl, or aryl substituted with alkyl,such as C₆-C₃₀ aryl optionally perfluorinated or optionally substitutedwith one or more C₁-C₁₆ alkyl groups, C₆-C₂₀ aryl optionallyperfluorinated or optionally substituted with one or more C₁-C₁₆ alkylgroups, and C₆-C₁₀ aryl groups optionally perfluorinated or optionallysubstituted with one or more C₁-C₁₆ alkyl groups; and

where DONOR is as defined below.

In one embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5.

In additional embodiments, the invention embraces compounds of Formula6, Formula 7, or Formula 8:

In the structures for Formula 6. Formula 7, and Formula 8 above:

M is selected from sulfur (S), oxygen (O), or N—R₁, where R₁ is H.C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer from 0 to 5 inclusive;

R₂ is selected from H, C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, C₂-C₁₆ alkenyl,and C₂-C₁₆ alkynyl;

J is selected from CH and N;

X is S, O, or NH when X is CH; and X is S when J is N;

R₆ is selected from aryl, perfluoroaryl, or aryl substituted with alkyl,such as C₆-C₃₀ aryl optionally perfluorinated or optionally substitutedwith one or more C₁-C₁₆ alkyl groups. C₆-C₂₀ aryl optionallyperfluorinated or optionally substituted with one or more C₁-C₁₆ alkylgroups, and C₆-C₁₀ aryl groups optionally perfluorinated or optionallysubstituted with one or more C₁-C₁₆ alkyl groups; and

where DONOR is as defined below.

In one embodiment, n is 0. In another embodiment, n is 1. In anotherembodiment, n is 2. In another embodiment, n is 3. In anotherembodiment, n is 4. In another embodiment, n is 5.

In additional embodiments, the invention embraces compounds of Formula9-10:

is selected from

where M is selected from sulfur (S), oxygen (O), or N—R₁, where. R₁ isH, C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer from 1 to 5 inclusive, and m is an integer from 0 to 5inclusive; and

where DONOR is as defined below.

In one embodiment, n is 1. In another embodiment, n is 2. In anotherembodiment, n is 3. In another embodiment, n is 4. In anotherembodiment, n is 5. In another embodiment, m is 0. In anotherembodiment, m is 1. In another embodiment, m is 2. In anotherembodiment, m is 3. In another embodiment, m is 4. In anotherembodiment, m is 5

In additional embodiments, the invention embraces compounds of Formula 9or Formula 10:

In the structures for Formula 9 and Formula 10 above:

M is selected, from sulfur (S), oxygen (O), or N—R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

n is an integer from 1 to 5 inclusive, and m is an integer from 0 to 5inclusive. In another embodiment, n is 1. In another embodiment, n is 2.In another embodiment, n is 3. In another embodiment, n is 4. In anotherembodiment, n is 5. In another embodiment, m is 0. In anotherembodiment, m is 1, In another embodiment, m is 2. In anotherembodiment, m is 3. In another embodiment, m is 4. In anotherembodiment, in is 5; and

where DONOR is as defined below.

In the structures for Formula 1-2-3-4-5, Formula 1, Formula 2, Formula3, Formula 4, Formula 5, Formula 6-7-8, Formula 6, Formula 7, Formula 8,Formula 9-10, Formula 9, and Formula 10 above, each DONOR moiety isindependently selected from the following group:

where X is C or Si;

A is N or P;

R₁₁ is selected from C₁-C₁₆ alkyl;

R₁₂ is selected from C₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀aryl substituted with one or more groups selected from —F, C₁-C₂₀ alkyl,C₁-C₂₀ fluoroalkyl, —O—C₁-C₂₀ alkyl, or —C₁-C₂₀ fluoroalkyl;

R₁₃ is selected from C₁-C₁₆ alkyl or C₆-C₂₀ aryl;

R₁₄ is selected from C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl, —C(═O)—O—C₁-C₁₆alkyl, or —O—C(═O)—C₁-C₁₆ alkyl; and

R₁₅ is selected from C₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀aryl substituted with one or more groups selected from —F, C₁-C₂₀ alkyl,C₁-C₂₀ fluoroalkyl, —O—C₁-C₂₀ alkyl, or −C₁-C₂₀ fluoroalkyl; and

R₁₆ is selected from C₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀aryl substituted with one or more groups selected from —F, C₁-C₂₀ alkyl,C₁-C₂₀ fluoroalkyl, —O—C₁-C₂₀ alkyl, or —C₁-C₂₀ fluoroalkyl.

In further embodiments, in the structure for Formula 1-2-3-4-5, eachDONOR moiety is the same moiety.

In further embodiments, in the structure for Formula 1, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 2, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 3, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 4, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 5, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 6-7-8, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 6, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 7, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 8, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 9-10, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 9, each DONORmoiety is the same moiety.

In further embodiments, in the structure for Formula 10, each DONORmoiety is the same moiety.

In additional embodiments, the invention embraces electronic andoptoelectronic devices comprising a non-polymeric compound, saidcompound incorporating one or more groups of Formula A:

where said non-polymeric compound is an electron acceptor or is anelectron donor in an active layer of the electronic or optoelectronicdevice, where M is selected from sulfur (S), oxygen (O), or N—R₁, whereR₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl and either X₁ is CH and Y₁ is N, orX₁ is N and Y₁ is CH. In one embodiment, where more than one moiety ofFormula A is present, M, X₁, and Y₁ for each moiety is chosenindependently of the other moiety or moieties. In another embodiment,where more than one moiety of Formula A is present, M is the same foreach moiety, X₁ is the same for each moiety, and Y₁ is the same for eachmoiety.

In additional embodiments, the invention embraces electronic andoptoelectronic devices comprising, a non-polymeric compound, saidnon-polymeric compound incorporating a pyridalthiadiazole group, apyridaloxadiazole group, or a pyridaltriazole group, wherein saidnon-polymeric compound is an electron acceptor or is an electron donorin an active layer of the electronic or optoelectronic device.

In additional embodiments, the invention embraces electronic andoptoelectronic devices utilizing the compounds described above.

In additional embodiments, the invention embraces optoelectronicdevices, such as organic solar cells, with the general devicearchitecture using the compounds described above as a light harvestingelectron donor, comprising:

1) a first hole-collecting electrode, optionally coated onto atransparent substrate;

2) an optional layer or layers adjacent to the first electrode, such asan electron-blocking, excitors-blocking, or hole-transporting layer;

3) a layer comprising a mixture of an electron acceptor, such as anorganic electron acceptor or an inorganic electron acceptor, and anorganic non-polymeric electron donor, said donor comprising one or morecompounds selected from Formula I, Formula Ia, Formula Ib, Formula Ic,Formula II, Formula IIa, Formula IIb, Formula IIc, Formula III, FormulaIIIa, Formula IIIb, Formula IIIc, Formula IIId, Formula IV-V, FormulaIV, Formula IVa, Formula IVb, Formula V, Formula Va, Formula Vb, FormulaVI-VII, Formula VI, Formula VIa, Formula VIb, Formula VII, Formula VIIa,Formula VIIb, Formula 1-2-3-4-5, Formula 1, Formula 2, Formula 3,Formula 4, Formula 5, Formula 6-7-8, Formula 6, Formula 7, Formula 8,Formula 9-10, Formula 9, or Formula 10;

4) an optional layer or layers such as hole-blocking, exciton-blocking,or electron-transporting layers; and

5) a second electron-collecting electrode.

In additional embodiments, the invention embraces optoelectronicdevices, such as organic solar cells, with the general devicearchitecture using the compounds described above as a light harvestingelectron acceptor, comprising:

1) a first hole-collecting electrode, optionally coated onto atransparent substrate;

2) an optional layer or layers adjacent to the first electrode, such asan electron-blocking, exciton-blocking, or hole-transporting layer;

3) a layer comprising a mixture of an electron donor, such as an organicelectron donor or an inorganic electron donor, and an organicnon-polymeric electron acceptor material selected from Formula I,Formula Ia, Formula Ib, Formula Ic, Formula II, Formula IIa, FormulaIIb, Formula IIc, Formula III, Formula IIIa, Formula IIIb, Formula IIIc,Formula IIId, Formula IV-V, Formula IV, Formula IVa, Formula IVb,Formula. V, Formula Va, Formula Vb, Formula VI-VII, Formula VI, FormulaVIa, Formula VIb, Formula VII, Formula VIIa, Formula VIIb, Formula1-2-3-4-5, Formula 1, Formula 2, Formula 3, Formula 4, Formula 5,Formula 6-7-8, Formula 6, Formula 7, Formula 8, Formula 940, Formula 9,or Formula 10;

4) an optional layer or layers such as hole-blocking, exciton-blocking,or electron-transporting layers; and 5) a second electron-collectingelectrode.

In additional embodiments, the invention embraces devices such asorganic field-effect transistors with the general device architectureusing the compounds described above as a hole transporting medium,comprising:

1) a dielectric substrate; in one embodiment, this dielectric substrateis Si/SiO₂;

2) an optional layer or layers adjacent the dielectric substrate, usedto modify the surface energy of the dielectric and/or to facilitatedeposition of the active layer; 3) an active layer comprising an organicnon-polymeric hole transporting material selected from Formula I,Formula Ia, Formula Ib, Formula Ic, Formula II, Formula IIa, FormulaIIb, Formula IIc, Formula III, Formula IIIa, Formula IIIb, Formula IIIc,Formula IIId, Formula IV-V, Formula IV, Formula IVa, Formula IVb,Formula V, Formula Va, Formula Vb, Formula VI-VII, Formula VI, FormulaVIa, Formula VIb, Formula VII, Formula VIIa, Formula VIIb, Formula1-2-3-4-5, Formula 1, Formula 2, Formula 3, Formula 4, Formula 5,Formula 6-7-8, Formula 6, Formula 7. Formula 8, Formula 9-10, Formula 9,or Formula 10; and

4) a metal electrode to facilitate charge injection and collection.

In additional embodiments, the invention embraces devices, such asorganic field-effect transistors with the general device architectureusing the compounds described above as an electron transporting medium,comprising:

1) a dielectric substrate; in one embodiment, this dielectric substrateis Si; SiO₂;

2) an optional layer or layers adjacent the dielectric substrate, usedto modify the surface energy of the dielectric and/or to facilitatedeposition of the active layer;

3) an active layer comprising an organic non-polymeric electrontransporting material selected from Formula I, Formula Ia, Formula Ib,Formula Ic, Formula II, Formula IIa, Formula IIb, Formula IIc, FormulaIII, Formula IIIa, Formula IIIb, Formula IIIc, Formula IIId, FormulaIV-V, Formula IV, Formula IVa, Formula IVb, Formula V, Formula Va,Formula Vb, Formula VI-VII, Formula VI, Formula VIa, Formula VIb,Formula VII, Formula VIIa, Formula VIIb, Formula 1-2-3-4-5, Formula 1,Formula 2, Formula 3, Formula 4, Formula 5, Formula 6-7-8, Formula 6,Formula 7, Formula 8, Formula 9-10, Formula 9, or Formula 10; and

4) a metal electrode to facilitate charge injection and collection.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a UV-VIS-NIR absorption spectrum of compound 101 in CHCl₃solution and of a film of compound 101 as-cast from CHCl₃ solution.

FIG. 2 shows a UV-VIS-NIR absorption spectrum of compound 102 in CHCl₃solution and of a film of compound 102 as-cast from CHCl₃ solution.

FIG. 3 shows a UV-VIS-NIR absorption spectrum of compound 103 in CHCl₃solution and of a film of compound 103 as-cast from CHCl₃ solution.

FIG. 4 shows a UV-VIS-NIR absorption spectrum of compound 104 in CHCl₃solution and of a film of compound 104 as-cast from CHCl₃ solution.

FIG. 5 shows a UV-VIS-NIR absorption spectrum of compound 105 in CHCl₃solution and of a film of compound 105 as-cast from CHCl₃ solution.

FIG. 6 shows a UV-VIS-NIR absorption spectrum of compound 106 in CHCl₃solution and of a film of compound 106 as-cast from CHCl₃ solution.

FIG. 7 shows a UV-VIS-NIR absorption spectrum of compound 107 in CHCl₃solution and of a film of compound 107 as-cast from CHCl₃ solution.

FIG. 8 shows a UV-VIS-NIR absorption spectrum of compound 108 in CHCl₃solution and of a film of compound 108 as-cast from CHCl₃ solution.

FIG. 9 shows a UV-VIS-NIR absorption spectrum of compound 109 in CHCl₃solution and of a film of compound 109 as-cast from CHCl₃ solution.

FIG. 10 shows a UV-VIS-NIR absorption spectrum of compound 110 in CHCl₃solution and of a film of compound 110 as-cast from CHCl₃ solution.

FIG. 11 shows a UV-VIS-NIR absorption spectrum of compound 111 in CHCl₃solution and of a film of compound 111 as-cast from CHCl₃ solution.

FIG. 12 shows a UV-VIS-NIR absorption spectrum of compound 112 in CHCl₃solution and of a film of compound 112 as-cast from CHCl₃ solution.

FIG. 13 shows a UV-VIS-NIR absorption spectrum of compound 113 in CHCl₃solution and of a film of compound 113 as-cast from CHCl₃ solution.

FIG. 14 shows a UV-VIS-NIR absorption spectrum of compound 114 in CHCl₃solution and of a film of compound 114 as-cast from CHCl₃ solution.

FIG. 15 shows a UV-VIS-NIR absorption spectrum of compound 115 in CHCl₃solution and of a film of compound 115 as-cast from CHCl₃ solution.

FIG. 16 shows a UV-VIS-NIR absorption spectrum of compound 116 in CHCl₃solution and of a film of compound 116 as-cast from CHCl₃ solution.

FIG. 17 shows a plot of HOMO-LUMO energy revels.

FIG. 18 shows energy levels of an organic solar cell device usingcompound 103.

FIG. 19 shows data for solar cells fabricated using compound 103, Activelayer thickness=75 nm. As-cast devices.

FIG. 20 shows data for solar cells fabricated using compound 103. Activelayer thickness=75 nm. Thermally annealed devices.

FIG. 21 shows data for solar cells fabricated using compound 103. Activelayer thickness=85 nm. As-cast devices.

FIG. 22 shows data for solar cells fabricated using compound 103. Activelayer thickness=85 nm. Thermally annealed devices.

FIG. 23 shows data for solar cells fabricated using compound 103 e layerthickness=105 nm. As-cast devices.

FIG. 24 shows data for solar cells fabricated using compound 103. Activelayer thickness=105 nm. Thermally annealed devices.

FIG. 25 shows data (current-voltage curves) for additional solar cellsfabricated using compound 103.

FIG. 26 shows data (EQE spectra) for additional solar cells fabricatedusing compound 103.

FIG. 27 shows data for 103:PC₇₁BM film blends.

DETAILED DESCRIPTION OF THE INVENTION

Definitions

“Alkyl” is intended to embrace a saturated linear, branched, cyclic, ora combination of linear and/or branched and/or cyclic hydrocarbonchains) and/or ring(s) having the number of carbon atoms specified, orif no number is specified, having 1 to 16 carbon atoms.

“Alkenyl” is intended to embrace a linear, branched, cyclic, or acombination of linear and/or branched and/or cyclic hydrocarbon chain(s)and/or ring(s) having at least one carbon-carbon double bond, and havingthe number of carbon atoms specified, or if no number is specified,having 2 to 16 carbon atoms.

“Alkynyl” is intended to embrace a linear, branched, cyclic, or acombination of linear and/or branched and/or cyclic hydrocarbon chain(s)and/or ring(s) having at least one carbon-carbon triple bond, and havingthe number of carbon atoms specified, or if no number is specified,having 2 to 19 carbon atoms, preferably 2 to 16 carbon atoms.

“Fluoroalkyl” indicates an alkyl group where at least one hydrogen ofthe alkyl group has been replaced with a fluorine substituent.

“Aryl” is defined as an optionally substituted aromatic ring system.Aryl groups include monocyclic aromatic rings, polyaromatic ringsystems, and polycyclic aromatic ring systems containing the number ofcarbon atoms specified, or if no number is specified, containing six tothirty carbon atoms. In other embodiments, aryl groups may contain sixto twenty carbon atoms six to twelve carbon atoms, or six to ten carbonatoms. In other embodiments, aryl groups can be unsubstituted.

“Heteroaryl” is defined as an optionally substituted aromatic ringsystem. Heteroaryl groups contain the number of carbon atoms specified,and one or more heteroatoms (such as one to six heteroatoms, or one tothree heteroatoms), where heteroatoms include, but are not limited to,oxygen, nitrogen, sulfur, and phosphorus. In other embodiments,heteroaryl groups may contain six to twenty carbon atoms and one to fourheteroatoms, six to twelve carbon atoms and one to three heteroatoms,six to ten carbon atoms and one to three heteroatoms, or three to sixcarbon atoms and one to three heteroatoms. In other embodiments,heteroaryl groups can be unsubstituted.

“Polymer” or “polymeric molecule” is defined herein as a structurecontaining at least eight repeating units. A “non-polymeric” molecule isa molecule containing seven or fewer repeating units. Thus, monomers,dimers, trimers, tetramers, pentamers, hexamers, and heptamers arenon-polymeric molecules for the purposes of this disclosure.Interruption of a repeating unit “resets” the count of subunits for thepurposes of this disclosure; thus, for example, for a molecule such asFormula 6:

when n is 5, the molecule is considered to have two separatefive-subunit pieces, that is, it is comprised of two pentamers ofthiophene, and is not considered a decamer or 10-subunit polymer ofthiophene.

Non-polymeric molecules typically have a discrete molecular weight,while polymeric molecules typically have a distribution of molecularweights due to varying numbers of monomers that are incorporated intothe growing chain during polymerization. Thus, in one embodiment, apreparation of a non-polymeric molecule will be characterized by asingle molecular weight (where the molecular weight is averaged onlyover isotopic variation due to differing isotopes such as hydrogen,deuterium, carbon-12, carbon-13, etc.) of about 90%, preferably 95%,more preferably 98%, still more preferably 99%, of the molecularspecies. In contrast, preparations of a polymeric molecule willtypically have a distribution of molecular weights due to varyingnumbers of monomers in the final polymer, where the molecular weight isan average over each individual polymeric species present in a givenpreparation (measured in either number-average molecular weight orweight-average molecular weight).

Small Molecule Chromophores

The current invention provides several advantages for preparation ofoptoelectronic devices. The organic materials described arenon-polymeric allowing for synthesis and purification producers to bemore repeatable than organic polymers. Unlike polymers, the organicmaterials described are discrete mono-disperse small molecules whichallows for their exact structure to be known and reproduced. Synthesisof organic small molecule chromophores containing the pyridalthiadiazole(PT, [1,2,5]thiadiazolo[3,4-c]pyridine) organic structure is facile.Preparation of the PT organic structure can be found in M. Leclerc etal. Journal of the American Chemical Society, 2008, 130, 732. Theasymmetry of the PT structure induced by the nitrogen atom in thearomatic backbone allows for facile mono-functionalization of the PTstructure, forgoing numerous synthetic steps and purification procedurescommon with related symmetric structures. The organic small moleculechromophores described herein have relatively planar structures allowingfor good inter-chromophore interaction, which facilitates chargetransfer and transport.

The electronic properties of the pyridalthiadiazole (PT,[1,2,5]thiadiazolo[3,4-c]pyridine) compounds are favorable. Thepyridalthiadiazole (PT, [1,2,5]thiadiazolo[3,4-c]pyridine) organicstructure has an ideal electron affinity. Donor-acceptor organicmaterials based on this unit have favorable frontier molecular orbitallevels (HOMO and LUMO) to accept and transport holes and electrons. Theorganic small molecule chromophores described also have favorablefrontier molecular orbital levels (HOMO and LUMO) for use as electrondonating materials in organic solar cell devices with fullerene,methanofullerene, rylene diimides or related π conjugated organicelectron acceptors. In addition, the organic small molecule chromophoresdescribed have favorable frontier molecular orbital levels (HOMO andLUMO) for use as electron accepting materials in organic solar celldevices with thiophene or phenyl based π-conjugated organic electrondonors.

The optical properties of the pyridalthiadiazole (PT,[1,2,5]thiadiazolo[3,4-c]pyridine) compounds are also very good. Theorganic small molecule chromophores described have broad absorptionspectra that absorb ultraviolet, visible, and near infrared radiation.The absorption spectra of the organic small molecule chromophoresdescribed have a favorable spectral overlap with the terrestrial solarspectrum, making them excellent light harvesting materials for organicsolar cells.

The compounds are also readily handled in solution, as the organic smallmolecule chromophores described retain good solubility in many commonorganic solvents. This allows solution processing during the preparationof the optoelectronic devices.

While solution processing is preferred for its ease of handling and lowcost, vapor deposition can also be used for PT, PO, or P3N molecules, ormixtures of said molecules with other components, which are suitable foruse in such a method (e.g., vacuum deposition, physical vapordeposition, chemical vapor deposition).

Device Architectures, Materials, and Fabrication

In one embodiment, the optoelectronic device of the invention comprisesthe following layers:

a) a first hole-collecting electrode, optionally coated onto atransparent substrate;

b) an optional layer or layers adjacent to the first electrode, such asan electron-blocking, exciton-blocking, or hole-transporting layer;

c) a layer comprising a mixture of an electron donor of the generalFormula I-VII and an electron acceptor (donor:acceptor);

d) an optional layer or layers such as hole-blocking, exciton-blocking,or electron-transporting layers; and

e) a second electron-collecting electrode.

Typically, the first electrode can be transparent, allowing light toenter the device, but in some embodiments, the second electrode can betransparent. In some embodiments, both electrodes are transparent.

Typically, the first electrode (layer “a”) is deposited onto asubstrate, and the device is fabricated by subsequent deposition oflayers “b” (if present), “c”, “d” (if present), and “e”. However, thesecond electrode “e” can be deposited onto a substrate, with subsequentdeposition of layers “d” (if present), “c”, “b” (if present), and “a”.

In another embodiment, the optoelectronic device of the inventioncomprises the following layers:

a) indium tin oxide (ITO) coated onto a transparent substrate (a firstelectrode), where the transparent substrate can be glass, plastic, orany other transparent material compatible with ITO;

b) poly(3,4-ethylene dioxythiophene:poly(styrenesulfonate) (PEDOT:PSS)or a electron-blocking, exciton-blocking, or hole-transporting metaloxide, including, but not limited to, MoO3,

c) a mixture of electron-donating chromophores of the general FormulaI-VII, and an electron-acceptor (donor:acceptor), and

e) a metal electrode (a second electrode); where layer (d) in theprevious embodiment is absent.

Typically, the first electrode (layer “a”) is deposited onto thesubstrate, and the device is fabricated by subsequent deposition oflayers “b”, “c”, and “e”. However, the second electrode “e” can bedeposited onto a substrate, with subsequent deposition of layers “c”,“b”, and “a”.

The PT, PO, or P3N electron donors or electron acceptors can be used intandem solar cells, such as those disclosed in US 2009/0126779. Tandemsolar cells are arranged so that light which is not absorbed by a firstsolar cell passes to a second solar cell, where the second solar celltypically has a smaller bandgap than the first solar cell in order toabsorb electromagnetic radiation that cannot be usefully absorbed by thefirst solar cell.

Passivating layers, such as those disclosed in US 2007/0221926 and US2007/0169816, can be incorporated into devices using the PT, PO, or P3Nelectron donors or electron acceptors.

Optical spacer layers, such as those disclosed in US 2006/0292736, canalso be employed in devices using the PT, PO, or P3N electron donors orelectron acceptors.

In one configuration, where light passes though a transparent firstelectrode (such as ITO-coated glass), it is absorbed by thedonor:acceptor mixture, which results in the separation of electricalcharges and migration of the charges to the electrodes, yielding ausable electrical potential.

The first electrode can be made of materials such as indium-tin oxide,indium-magnesium oxide, cadmium tin-oxide, tin oxide, aluminum- orindium-doped zinc oxide, gold, silver, nickel, palladium and platinum.Preferably the first electrode has a high work function (4.3 eV orhigher). Preferably, the first electrode is transparent.

The optional layer adjacent to the first electrode is preferablypolystyrenesulfonic acid-doped polyethylenedioxythiophene (PEDOT:PSS).Other hole transporting materials, such as polyaniline (with suitabledopants), orN,N′-diphenyl-N,N′-bis(3-methylphenyl)[1,1′-biphenyl]-4,4-′-diamine(TPD), nickel oxide, can be used. Electron-blocking, exciton-blocking,or hole-transporting metal oxides, such as MoO₃, MoO_(3-x), V₂O_(5-x),NiO, Ta₂O₅, Ag₂O, CuO, Cu₂O, CrO_(3-x), and WO₃, where x is between 0.01and 0.99, more preferably between 0.1 and 0.9, can be used as materialsbetween the hole-transporting electrode and the active layer. Othersuitable materials are described in Greiner, Mark T. et al., “Universalenergy-level alignment of molecules on metal oxides,” Nature Materials,DOI: 10.1038/NMAT3159 (Nov. 6, 2011).

One method of fabricating the optoelectronic device is as follows: Aconductive, transparent substrate is prepared from commerciallyavailable indium tin oxide-coated glass and polystyrenesulfonic aciddoped polyethylenedioxythiophene using standard procedures. A solutioncontaining a mixture of the donor and acceptor materials is prepared sothat the ratio of donor to acceptor is between 1:99 and 99:1 parts bymass; more preferably between 3:7 and 7:3 parts by mass. The overallconcentration of the solution may range between 0.1 mg/mL, and 100mg/mL, but is preferably in the range of 10 mg/mL and 30 mg/mL. In inone embodiment of the invention, PT, PO, or P3N non-polymeric moleculesare used that have a solubility of at least about 0.1 mg/mL in anorganic solvent, 1 mg/mL in an organic solvent, 5 mg/mL, 10 mg/mL in anorganic solvent, 30 mg/mL in an organic solvent, or 100 mg/mL in anorganic solvent. The organic solvent can be selected from chloroform,toluene, chlorobenzene, methylene dichloride, tetrahydrofuran, or carbondisulfide.

The electron acceptor is preferably [6,6]-phenyl C61-butyric acid methylester (PCBM), but may be a different fullerene (including, but notlimited to, C71-PCBM), a tetracyanoquinodimethane, a vinazene, aperylene, tetracarboxylic acid-dianhydride, a perylene tetracarboxylicacid-diimide, an oxadiazole, carbon nanotubes, or any other organicelectron acceptor, such as those compounds disclosed in U.S.2008/0315187.

In other embodiments, the electron acceptor is an inorganic acceptorselected from TiO₂ (titanium dioxide), TiO_(x) (titanium suboxide, wherex<2) and ZnO (zinc oxide). The titanium dioxide can be anatase, rutile,or amorphous. A titanium dioxide layer can be prepared by depositing asol-gel precursor solution, for example by spincasting or doctorblading,and sintering at a temperature between about 300° C. and 500° C. When aninorganic layer is used, component (c) of the optoelectronic devicedescribed above can be comprised of a layer of electron-donatingchromophores of the general Formula I-VII and an inorganicelectron-acceptor layer. Alternatively, the inorganic material can bedispersed in the electron-donating chromophores to create a singlelayer. Preparation of TiO₂ for use in solar cells is described in BrianO'Regan & Michael Grätzel, Nature 353:737 (1991) and Scrap Günes et al.,2008 Nanotechnology 19 424009.

When titanium suboxide according to the formula TiO_(x) where x<2, isused, x is preferably 1<x<1.98, 1.1<x<1.9, 1.2<x<1.8, or 1.3<x<1.8. X inthe formula TIO_(x) can be <2, <1.98, <1.9, <1.8, <1.7, or <1.6.

Useful solvents include chloroform, toluene, chlorobenzene, methylenedichloride, tetrahydrofuran, and carbon disulfide. However, the solventused may be any solvent which dissolves or partially dissolve both donorand acceptor materials and has a non-zero vapor pressure.

The solution of donor and acceptor is deposited by spin casting,doctor-blading, ink-jet printing, roll-to-roll coating, slot-dyecoating, gravure coating, or any process which yields a continuous filmof the donor-acceptor mixture such that the thickness of the film iswithin the range of 10 to 1000 nm, more preferably between 50 and 150nm.

In certain embodiments, the layer of the donor and acceptor is cast froma solution comprising a solvent and the electron donor and the electronacceptor. The solvent can comprise chloroform, thiophene,trichloroethylene, chlorobenzene, carbon disulfide, a mixture of any ofthe foregoing solvents or any solvent or solvent mixture that dissolvesboth the donor and acceptor organic small molecule. The solvent can alsoinclude processing additives, such as those disclosed in US PatentApplication Publication Nos. 2009/0032808, 2008/0315187, or2009/0108255. For example, 1,8-diiodooctane (DIO) can be added to thesolvent/donor/acceptor mixture in an amount of 0.1-10% by volume. Theadditive, such as 2% DIO, can be added to any organic solvent used tocast the layer of donor/acceptor, such as chloroform. The solvent canalso include doping agents such as molybdenum trioxide (MoO₃). Forexample, MoO₃ can be added to the solvent/donor/acceptor mixture in anamount of 0.1-10% by volume.

An additional layer or layers of material (i.e., the layer(s) adjacentto the second electrode) may optionally be deposited on top of thedonor-acceptor film in order to block holes or excitons, act as anoptical buffer, or otherwise benefit the electrical characteristics ofthe device. 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline can act as ahole-blocking or exciton-blocking material, while4,4′4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine, andpolyethylene dioxythiophene can act as exciton-blocking materials. Othermaterials that can be used between the second electrode and the activelayer are titanium suboxide, ZnO, Cs₂CO₃, and ZrO₃. Additional materialssuitable for use are described in Greiner, Mark T. et al., “Universalenergy-level alignment of molecules on metal oxides,” Nature Materials,DOI: 10.1038/NMAT3159 (Nov. 6, 2011).

Finally, an electrode, such as a metal electrode, is deposited on top ofthe structure by thermal evaporation, sputtering, printing, laminationor some other process. Conducting metal oxides, such as indium tinoxide, zinc oxide, or cadmium oxide, can also be used as electrodes, aswell as conducting organic materials, such as electrodes comprisinggraphene. For metal electrodes, the metal is preferably aluminum, silveror magnesium, but may be any metal. Nanowires such as silver nanowirescan also be used. If a transparent electrode is desired, very thinmetallic sheets of metals can also be used. In some embodiments, thedevice is annealed before and/or after evaporation of the metalelectrode.

Hole and electron mobilities are important parameters to consider in thefabrication/function of bulk heterojunction solar cells. For optimaldevice performance, a balance in the mobility of both charge carriers isdesirable. Preferably, the electron and hole mobilities are both on theorder of 10⁻⁴ cm²/Vs or higher. More preferably, the electron mobilitiesare on the order of 10⁻³ cm²/Vs or higher. In some embodiments, theelectron mobilities are on the order of 10⁻⁴ cm²/Vs or higher, and thehole mobilities are between 10⁻⁸ cm²/Vs and 10⁻⁴ cm²/Vs or higher. Inother embodiments, the electron mobilities are on the order of 10⁻³cm²/Vs or higher, and the hole mobilities are between 10⁻⁸ cm²/Vs and10⁻⁴ cm²/Vs or higher.

Optoelectronic devices of the present invention have excellentphotovoltaic properties. In some embodiments, the power conversionefficiency (PCE) is at least 0.5%, at least 1.0%, at least 2.0%, or atleast 3.0%. In some embodiments, the short circuit current density isgreater than 3.0 mA/cm², and preferably greater than 8 mA/cm². In someembodiments, the open circuit voltage is between 0.3 and 1.0 V orhigher. In some embodiments, the device exhibits an external quantumefficiency of approximately 35% or greater between 300 and 800 nm.

The morphological properties of the donor:acceptor films can be measuredusing atomic force microscopy or other surface-sensitive techniques.Preferably, the films will have a root-mean-squared surface roughness ofless than 1.0 nm, more preferably less than 0.5 nm.

For embodiments of the devices using an inverted device architecture,the first electrode can comprise Au or another material having a workfunction higher than the work function of the second electrode, whilethe second electrode can comprise an ITO substrate modified using aself-assembled monolayer of 3-aminopropyltrimethoxysiloxane or anothermaterial having a work function lower than the work function of thefirst electrode.

EXAMPLES General Experimental Procedures

General Data: Preparations were carried out on a bench top or under anatmosphere of dry, O₂-free N₂ employing both Schlenk line techniques anda Vacuum Atmospheres inert atmosphere glove box. Solvents (toluene,xylenes) were dried over sodium/benzophenone, distilled under vacuum,and stored over molecular sieves (4 Å). Solvents (chloroform) were driedover calcium hydride, distilled under vacuum, and stored over molecularsieves (4 Å). Molecular sieves (4 Å) were purchased from AldrichChemical Company and dried at 140° C. tinder vacuum for 24 hours priorto use. Deuterated solvents were dried over CaH₂ (CDCl₃) All reactantsand reagents are commercially available and used as received unlessotherwise noted.

Materials: Compound5,5′-Bis(trimethylstannyl)-3,3′-di-2-ethylhexylsilylene-2,2′-bithiophene{DTS(SnMe₃)₂} (Hou, J. H.; Chen, H. Y.; Chang, S. Q,; Li, G.; Yang, Y.Journal of the American Chemical Society 2008, 130, 16144-16145) and5′-Hexyl-2,2′-bithiophene-5-trimethylstannane (Parab, K.;Venkatasubbaiah, K.; Jakle, F. Journal of the American Chemical Society2006, 128, 12879-12885) were prepared by methods similar to thosereported in the literature. Compounds5,5′-dibromo-3,3′-di-2-ethylhexylsilylene-2,2′-bithiophene (DTS-Bin) and4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂) were purchased fromLuminescence Technology Corp. (Lumtec) and used as received.

NMR: ¹H and ¹³C nuclear magnetic resonance (NMR) spectroscopy spectrawere recorded on a Bruker Avance-500 MHz spectrometer at 25° C. unlessotherwise noted. ¹H and ¹³C NMR spectra are referenced to SiMe₄ usingthe residual solvent peak impurity of the given solvent. Chemical shiftsare reported in ppm and coupling constants in Hz as absolute values.DEPT, ¹H-¹H and ¹H-¹³C correlation experiments were completed forassignment of the carbon atoms. ¹H-¹H NOE experiments were carried outwith a mixing time of 0.8 seconds.

UV-vis-nearIR: UV-visible spectra were recorded using either a BeckmanCoulter DU 800 series or Perkin Elmer Lambda 750 spectrophotometer atroom temperature unless otherwise noted. All solution UV-vis experimentswere run in CHCl₃ under an N₂, atmosphere in Teflon-capped 1 mm quartzcuvettes. Films were prepared by spin-coating a 1% (w/w) solution of acompound of the invention, or a compound of the invention with PC₇₁BM,from CHCl₃ onto quartz substrates.

CHN: Combustion analyses were performed by the MST analytical lab at theUniversity of California, Santa Barbara.

Electrochemistry: All electrochemical measurements were performed usingCHI instrument model 730B in a standard three-electrode, one compartmentconfiguration equipped with Ag/AgCl electrode, Pt wire and Glassy carbonelectrode (dia, 3 mm), as the pseudo reference, counter electrode andworking electrode respectively. Glassy carbon electrodes were polishedwith alumina. The cyclic voltammetry (CV) experiments were performed inanhydrous acetonitrile (AcCN) solution with 0.1 M tetrabutylammoniumhexafluorophosphate (TBAPF₆) as the supporting electrolyte at scan rate100 mV/s unless otherwise stated. All electroChemical solutions werepurged with dry Ar for 15 minutes at least to deoxygenate the system.Under these conditions, a Fc/Fc⁺ standard was calibrated to be 0.48 V. Amixture of small molecule in dry CHCl₃ (˜3 ma/mL) was used forpreparation films at room temperature. Films were prepared by drop-castonto Glassy carbon electrode for CV measurement.

Example 1

Synthesis of 7-bromo-4-thienyl[1,2,5]thiadiazolo[3,4-c]pyridine(ThPTBr): A 20 mL microwave tube was charged with4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 1.51 g, 5.12 mmol),2-(tributylstanayl)thiophene (Bu₃Sn—Th, 1.99 g, 5.33 mmol), Pd(PPh₃)₄.(0.050 g, 0.04 mmol), toluene (10 mL), and sealed with a Teflon® cap.The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3minutes, and 175° C. for 40 minutes, using a Biotage microwave reactor.Upon cooling, the residue was passed through a short silica plug elutingwith CH₂Cl₂ (500 mL). All volatiles were removed in vacuo to give thecrude product as an orange solid. The solid was slurried in MeOH (300mL), sonicated for 10 minutes, and filtered. The solid was washed withcopious amounts of MeOH and then dried under vacuum for 24 hours. Theproduct was collected as an orange solid. Recovered yield: 920 mg (60%).

¹H NMR (CD₂Cl₂): δ 8.67 (dd, ³J_(H-H)=4 Hz, ⁴J_(H-H)=1 Hz, 1H, Th-CH),8.63 (s, 1H, PT-CH), 7.64 (dd, ³J_(H-H)=4 Hz, ⁴J_(H-H)=1 Hz 1H, Th-CH),7.26 (dd, ³J_(H-H)=5 Hz. ³J_(H-H)=4 Hz 1H, Th—CH), ¹³C{¹H}NMR (CD₂Cl₂):156.90, 148.46, 147.96 (s, quaternary), 146.18 (s, CH), 141.65 (s,quaternary), 133.09 (s, CH), 131.74 (s, CH), 129.57 (s, CH), 108.91 (s,quaternary). Anal. Calcd. for C₉H₄BrN₃S₂: C, 36.25; H, 1.35; N. 14.09.Found: C, 36.6; H, 1.35; N, 13.8%. HRMS (EI) m/z, calcd for C₁₃H₇N₃S₃(M⁺): 298.9; found: 299.

Synthesis of 101: A 20 mL microwave tube was charged with5,5′-Bis(trimethylstannyl)-3,3′-Di-2-ethylhexylsilylene-2,2′-bithiophene(M₃Sn—SD_(TEH)-SnM_(e3), 961 mg, 1.29 mmol),7-bromo-4-thienyl[1,2,5]thiadiazolo[3,4-c]pyridine (ThPTBr, 770 mg, 2.58mmol), Pd(PP₃₎₄ (0.050 g, 0.04 mmol), toluene (15 mL), and sealed with aTeflon® cap. The reaction mixture was heated to 12° C. for 3 minutes,14° C. for 3 minutes, and 17° C. for 60 minutes, using a Biotagemicrowave reactor. Upon cooling, the residue was passed through a shortsilica plug eluting with CHC₁₃. (5% E_(t3)N) (500 mL). All volatileswere removed in vacuo to give the crude product as a purple solid. Thematerial was then loaded onto silica and purified by flashchromatography using a hexanes/CHCl₃ (5% E_(t3)N) gradient. Afterfraction collection and solvent removal a purple solid was obtained. Thesolid was slurried in MeOH (300 mL), sonicated for 10 minutes, andfiltered. The solid was washed with copious amounts of MeOH and thendried under vacuum for 24 hours. The product was collected as purplesolid. Recovered yield: 980 mg (88%). ¹H NMR (C_(D2)C₁₂); δ 8.74 (s, 2H,PT-CH), 8.63 (d, ³ _(JH-H)=4 Hz, 2H Th-CH), 8.25 (t, 2H, SDT-CH), 7.60(d, ³ _(JH-H)=4 Hz, 2H Th-CH), 7.27 (dd, ³ _(JH-H)=5 Hz, ³J_(H-H)=4 Hz2H, Th-CH), 1.59 (h, ³J_(H-H)=6 Hz, 2H, CH), 1.38 (m, 4H, C_(H2)), 1.32(m, 4H, C_(H2)), 1.25 (m, 8H, C_(H2)), 1.16 (m, 4H, SiC_(H2)), 0.86 (t,³J_(H-H)=8 Hz, 6H, C_(H3)), 0.83 (t, ³ _(JH-H)=8 Hz, 6H, C_(H3)).¹³C^({1)H}NMR (C_(D2)C₁₂): 155.06, 151.01, 148.44, 145.97, 142.57 (s,quaternary), 140.42 (s, CH), 139.02, 132.07 (s, CH), 131.79 (s, SDT-CH),130.81 (s, CH), 129.37 (s, CH), 121.39 (s, quaternary), 36.70 (s, CH),36.40 (s, SiC_(H2)), 29.59 (s, 2×C_(H2)), 23.62 (s, C_(H2)), 18.28 (s,C_(H2)), 14.54 (s, C_(H3)), 11.24 (s, C_(H3)) Anal. Calcd. for_(c421144N6S6)Si: C, 59.12; H, 5.20; N, 9.85. Found: C, 59.0; H, 4.31;N, 9.32%. HRMS (EI) m/z, calcd for _(c42H44N6S6)Si (^(M+)): 852; found:852. Absorbance: (CHC₁₃) λ_(max)=582 nm, λ_(onset)=678 nm. (As CastFilm) λ_(max)=604, 652 nm, λ_(onset)=736 nm.

The UV-VIS-NIR absorption spectrum of 101 in CHCl₃ solution and of afilm of 101 as-cast from CHCl₃ solution is shown in FIG. 1.

Example 2

Synthesis of7-bromo-4-(5-hexylthiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine(HexThPTBr): In a N₂ filled glove box a 20 mL glass tube was chargedwith 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 1.41 g, 4.78 mmol),(5-hexylthiophen-2-yl)trimethylstannane (1.58 g, 4.78 mmol), Pd(PPh₃)₄(0.025 g, 0.02 mmol), toluene (15 mL), and sealed with a Teflon® cap.The reaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3minutes, and 175° C. for 30 minutes, using a Biotage microwave reactor.Upon cooling, the residue was passed through a short silica plug elutingwith CHCl₃ (5% Et₃N) (500 mL), All volatiles were removed in vacuo togive the crude product as a red tacky solid. MeOH (100 mL) was added andthe mixture sonicated for 5 minutes, followed by removal of MeOH invacuo. The product was then slurried in MeOH (200 mL), filtered, washedwith MeOH (200 mL), and dried under high vacuum for 24 hours. Theproduct was collected as red solid. Recovered yield: 1.7 mg (94%), ¹HNMR (CDCl₃): δ 8.62 (s, 1H, PT-CH), 8.51 (d, 1H, ³J_(H-H)=5 Hz, Th-CH),6.94 (d, 1H, ³J_(H-H)=5 Hz, Th-CH), 2.90 (t, 2H, ³J_(H-H)=8 Hz, Th-CH₂),1.71 (tt, 2H, ³J_(H-H)=8 Hz, CH₂), 1.42 (br m, 2H, CH₂), 1.33 (br m, 4H,CH₂), 0.90 (m, 3H, ³J_(H-H)=8 Hz, CH₃). ¹³C{¹H}NMR (CDCl₃): 156.31,153.21, 147.92, 47.65 (s, quaternary), 145.82 (s, CH), 138.19 (s,quaternary), 133.15, 126.56 (s, CH), 107.48 (s, quaternary), 31.53 (s,CH₂), 31.36 (s, CH₂), 30.58 (s, CH₂) 28.75 (s, CH₂), 22.54 (s, CH₂),14.05 (s, CH₃). Anal. Calcd. for C₁₅H₁₆BrN₃S₂: C, 47.12; H, 4.22; N,10.99. Found: C, 47.4; H, 4.03; N, 10.6%.

Synthesis of 102: In a N₂ filled glove box a 20 mL microwave tube wascharged with5,5′-Bis(trimethylstannyl)-3,3′-di-2-ethylhexylsilylene-2,2′-bithiophene(Me₃Sn-SDT_(EH)-SnMe₃, 510 mg, 0.68 mmol),7-bromo-4-(5-hexylthiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine(HexThPTBr, 574 mg, 1.50 mmol.), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene(15 mL), and sealed with a Teflon® cap. The reaction mixture was heatedto 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 120minutes, using a Biotage microwave reactor. Upon cooling, the residuewas passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500mL). All volatiles were removed in vacuo to give the crude product as apurple solid. The material was then loaded onto silica and purified byflash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. Afterfraction collection and solvent removal a purple solid was obtained.Purification by silica column chromatography was carried out twice. Thesolid was slurried in MeOH (300 mL), sonicated for 10 minutes, andfiltered. The solid was washed with copious amounts of MeOH and thendried under vacuum for 24 hours. The product was collected as purplesolid. Recovered yield: 562 mg (80%). ¹H NMR (CDCl₃): δ 8.70 (s, 2H,PT-CH), 8.43 (d, ³J_(H-H)=5 Hz, 2H, Th-CH), 8.18 (t, 2H, SDT-CH), 6.93(d, ³J_(H-H)=5 Hz, 2H, Th-CH), 2.92 (t, ³J_(H-H)=7 Hz, 4H Th-CH₂), 1.79(tt, ³J_(H-H)=7 Hz, 4H, CH₂), 1.59 (br m, 2H, CH), 1.44 (br m, 4H, CH₂),1.35 (m, 14H, CH₂), 1.25 (m, 8H, CH₂), 1.19-1.08 (m, 4H, SiCH₂). 0.92(m, 6H, CH₃), 0.88-0.83 (m, 12H, CH₃). ¹³C{¹H} NMR (CDCl₃): 154.51,152.09, 150.27, 147.90, 145.05 (s, quaternary), 140.09 (s, CH), 139.23,138.53 (s, quaternary), 132.03 (s, CH), 130.88 (s, CH), 126.40 (s, CH,120.22 (s, quaternary), 36.08 (s, CH). 35.83 (s, CH₂), 31.61 (s, SiCH₂),31.45 (s, CH₂), 30.62 (s, ThCH₂), 29.05 (s, CH₂), 28.98 (s, CH₂), 28.83(s, CH₂), 23.08 (s, CH₂), 22.60 (s, CH₂), 17.79 (s, CH₂), 14.24 (s,CH₃), 14.10 (s, CH₃), 10.89 (s, CH₃), Anal. Calcd. for C₅₄H₆₈N₆S₆Si: C,63.48; H, 6.71; N, 8.23. Found: C, 63.5; H, 6.65; N, 8.20%. Absorbance:(CHCl₃) λ_(max)=600 nm, λ_(onset)=700 nm. (As Cast Film) λ_(max)=620,670 nm, λ_(onset)=760 nm.

The UV-VIS-NIR absorption spectrum of 102 in CHCl₃ solution and of afilm of 102 as-cast from CHCl₃ solution is shown in FIG. 2.

Example 3

Synthesis of7-bromo-4-5-(5-hexylthiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine(HexThThPTBr): Suzuki: In a N₂ filled glove box a 20 mL glass tube wascharged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTB₂, 550 mg, 1.86mmol), Na₂CO₃ (1 g), Pd(PPh₃)₄ (0.050 g, 0.04 mmol), anhydrous THF (10mL), and sealed with a Teflon® cap. To this mixture was added de-gassedde-ionized water (5 mL) under Ar and the mixture stirred for 5 minutes.5′-Hexyl-2,2′-bithiophene-5-boronic acid pinacol ester (773 mg, 2.05mmol) in anhydrous THF (5 mL) was then added to the reaction mixturewhich was subsequently purged with Ar for 5 minutes. The reactionmixture was heated to 90° C. and vigorously stirred for 16 hours. Uponcooling the reaction mixture was poured into 500 mL of a 1:1 MeOH/H₂Osolution and stirred for 20 minutes. The precipitate that formed wascollect by filtration and washed with 500 mL of a 2:1 MeOH/H₂O solutionand 100 mL of MeOH. The crude product was purified, by flashchromatography eluting with a hexanes/CHCl₃ gradient. After fractioncollection and solvent removal the resulting red solid was dried underhigh vacuum for 48 hours. The product was collected as red solid.Recovered yield: 555 mg (65%). Stille: In a N₂ filled glove box a 5 mLglass tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole(PTBr₂, 550 mg, 1.86 mmol),5′-Hexyl-2,2′-bithiophene-5-trimethylstannane (770 mg, 1.86 mmol),Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (4 mL), and sealed with aTeflon® cap. The reaction mixture was heated to 120° C. for 3 minutes,140° C. for 3 minutes, and 175° C. for 25 minutes, using a Biotagemicrowave reactor. Upon cooling, the residue was passed through a shortsilica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles wereremoved in vacuo to give the crude product as a red solid. The productwas slurried in MeOH (200 mL), filtered, washed with MeOH (20 mL), anddried under high vacuum for 24 hours. The product was collected as redsolid. Recovered yield: 750 mg (87%), ¹H NMR (CDCl₃): δ 8.62 (s, 1H,PT-CH), 8.56 (d, 1H, ³J_(H-H)=5 Hz, Th—CH), 7.21 (m, 1H, Th-CH), 7.17(m, 1H, Th-CH), 6.74 (m, Th-CH), 2.83 (d, 2H, ³ _(H-H)=8 Hz, Th-CH₂),1.71 (m, 2H. CH₂), 1.41 (m, 2H, CH₂), 1.33 (m, 4H, CH₂), 0.92 (m, 3H,CH₃). ¹³C{¹H} NMR (CDCl₃): 147.44, 147.26 (s, quaternary), 145.85 (s,CH), 143.86, 138.48, 134.32 (s, quaternary), 133.79 (s, CH), 128.63 (s,quaternary), 125.00, 124.58 (5, CH), 124.07 (s, quaternary), 31.57 (5,CH₂), 31.52 (s, CH₂), 30.30 (s, CH₂), 28.80 (s, CH₂), 22.61 (s, CH₂),14.12 (s, CH₃), Anal. Calcd. for C₁₉H₁₈BrN₃S₃: C, 49.13; H, 3.91; N,9.05, Found: C, 48.8; H, 3.60; N, 9.01%.

Synthesis of 103: In a N₂ filled glove box a 20 mL microwave tube wascharged with5,5′-Bis(trimethylstannyl)-3,3′-Di-2-ethylhexylsilylene-2,2′-bithiophene(Me₃Sn-SDT_(EH)-SnMe₃, 617 mg, 0.83 mmol), 7-bromo 4-(5-(5hexylthiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine(HexThThPTBr, 770 Mg, 1.66 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol),toluene (15 mL), and sealed with a Teflon® cap. The reaction mixture washeated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for120 minutes, using a Biotage microwave reactor. Upon cooling, theresidue was passed through a short silica plug eluting with CHCl₃ (5%Et₃N) (500 mL). All volatiles were removed in vacuo to give the crudeproduct as a purple solid. The material was then loaded onto silica andpurified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N)gradient. After fraction collection and solvent removal a purple solidwas obtained. Purification by silica column chromatography was carriedout twice. The solid was slurried in MeOH (300 mL), sonicated for 10minutes, and filtered. The solid was washed with copious amounts of MeOHand then dried under vacuum for 24 hours. The product was collected aspurple solid. Recovered yield: 700 mg (71%). ¹H NMR (CDCl₃): δ 8.79 (s,2H, PT-CH), 8.55 (d, ³J_(H-H)5 Hz, 2H, Th-CH), 8.17 (t, 2H, SDT-CH),7.23 (d, ³J_(H-H)=5 Hz, 2h Th-CH), 7.20 (d, ³J_(H-H)=5 Hz, 2H Th-CH),6.75 (m, 2H, Th-CH), 2.84 (t, ³J_(H-H)=7 Hz, 411 Th-CH₂), 1.74 (h,³J_(H-H)=6 Hz, 4H, CH), 1.60 (m, 2H, CH), 1.43 (m, 4H, CH₂), 1.31 (m,14H, CH₂), 1.24 (m, 10H, CH₂), 1.13 (m, 4H, SiCH₂), 0.92 (m, 6H, CH₃),0.85 (m, 12H, CH₃). ¹³C{¹H} NMR (CDCl₃): 154.55, 150.50, 148.03, 146.99,145.19, 142.82 (s, quaternary), 140.17 (s, CH), 139.66, 138.58, 134.62(s, quaternary), 132.70 (s, CH), 130.87 (s, CH), 125.22 (s, CH), 124.66(s, CH), 124.60 (s, CH), 120.47 (s, quaternary), 36.05 (s, CH), 35.79(s, CH₂), 31.57 (s, SiCH₂), 31.54 (s, CH₂), 30.29 (s, ThCH₂), 29.02 (s,CH₂), 28.99 (s. CH₂), 28.78 (s, CH₂), 23.05 (s, CH₂), 22.58 (s, CH₂),17.75 (s, CH₂), 14.21 (s, CH₃), 14.08 (s, CH₃), 10.87 (s, CH₃). Anal.Calcd. for C₆₂H₇₂N₆S₈Si: C, 62.79; H, 6.12; N, 7.09. Found: C, 62.5; H,6.00; N, 7.05%. HRMS (EI) m/z, calcd for C₆₂H₇₂N₆S₈Si (M⁺): 1184; found:1184. Absorbance: (CHCl₃) λ_(max)=625 nm. λ_(onset)=725 mm, ε=35000cm⁻¹M⁻¹. (As Cast Film) λ_(max)=655, 710 nm, λ_(onset)=795 nm.

The UV-VIS-NIR absorption spectrum of 103 in CHCl₃ solution and of afilm of 103 as-cast from CHCl₃ solution is shown in FIG. 3.

Example 4

Synthesis of7-bromo-4-(5-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine(HexThThThPTBr): Suzuki: In a N₂ filled glove box a 20 mL glass tube wascharged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 470 mg, 1.59mmol), Na₂CO₃ (Ig), Pd(PPh₃)₄ (0.050 g, 0.01 mmol), anhydrous THF (10mL), and sealed with a Teflon® cap. To this mixture was added de-gassedde-ionized water (5 mL) under Ar and the mixture stirred for 5 minutes.5′Hexyl-2,2′,2″-trithiophene-5-boronic acid pinacol ester (729 mg, 1.59mmol) in anhydrous THF (5 mL) was then added to the reaction mixturewhich was subsequently purged with Ar for 5 minutes. The reactionmixture was heated to 90° C. and vigorously stirred for 16 hours. Uponcooling the reaction mixture was poured into 500 mL of a 1:1 MeOH/H₂Osolution and stirred for 20 minutes. The precipitate that formed wascollect by filtration and washed with 500 mL of a 2:1 MeOH/H₂O solutionand 100 mL of MeOH. The crude product was purified by flashchromatography eluting with a hexanes/CH₂Cl₂ gradient. After fractioncollection and solvent removal the resulting red solid was dried underhigh vacuum for 48 hours. The product was collected as red solid.Recovered yield: 400 mg (46%). Stille: In a N₂ filled glove box a 5 mLglass tube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole(PTBr₂, 197 mg, 0.67 mmol),5′-Hexyl-2,2′,2″-trithiophene-5-trimethylstannane (330 mg, 0.067 mmol),Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (4 mL), and sealed with aTeflon® cap. The reaction mixture was heated to 120° C. for 3 minutes,140° C. for 3 minutes, and 175° C. for 60 minutes, using a Biotagemicrowave reactor. Upon cooling, the residue was passed through a shortsilica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles wereremoved in vacuo to give the crude product as a red solid. The productwas slurried in MeOH (200 mL), filtered, washed with MeOH (200 mL), anddried under high vacuum for 24 hours. The product was collected as redsolid. Recovered yield: 310 mg (85%). ¹H NMR (CDCl₃): δ 8.64 (s, 1H,PT-CH), 8.59 (d, 1H, ³J_(H-H)=5 Hz, Th-CH), 7.26 (d, 1H, ³J_(H-H)=5 Hz,Th-CH), 7.24 (d, 1H, ³J_(H-H)=5 Hz, Th-CH), 7.05 (d, 1H, ³J_(H-H)=5 Hz,Th-CH), 7.03 (d, 1H, ³J_(H-H)=5 Hz, Th-CH), 6.71 (d, ³J_(H-H)=5 Hz,Th-CH), 2.80 (m, 2H, Th-CH₂), 1.67 (m, 2H, CH₂), 1.41 (m, 2H. CH₂), 1.34(m, 4H, CH₂), 0.92 (m, 3H, CH₃).

Synthesis of 104: In a N₂ filled glove box a 20 mL microwave tube wascharged with5,5′-Bis(trimethylstannyl)-3,3′-Di-2-ethylhexylsilylene-2,2′-bithiophene(Me₃Sn-SDT_(LH)-SnMe₃, 188 mg, 0.25 mmol),7-bromo-4-(5-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine(HexThThThPTBr, 290 mg, 0.53 mmol), Pd(PPh₃)₄. (0.025 g. 0.02 mmol),toluene (15 mL), and sealed with a Teflon® cap. The reaction mixture washeated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for120 minutes, using a Biotage microwave reactor. Upon cooling, theresidue was passed through a short silica plug eluting with CHCl₃ (5%Et₃N) (500 mL). All volatiles were removed in vacuo to give the crudeproduct as a purple solid. The material was then loaded onto silica andpurified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N)gradient. After fraction collection and solvent removal a purple solidwas obtained. Purification by silica column chromatography was carriedout twice. The solid was slurried in MeOH (300 mL), sonicated for 10minutes, and filtered. The solid was washed with copious amounts of MeOHand then dried under vacuum for 24 hours. The product was collected aspurple solid. Recovered yield: 250 mg (73%). ¹H NMR (CDCl₃): δ 8.74 (s,2H, PT-CH), 8.50 (d, ³J_(H-H)=5 Hz, 2H, Th-CH), 8.14 (t, 2H, SDT-CH),7.23 (d, ³J_(H-H)=5 Hz, 2H Th-CH), 7.21 (d, ³J_(H-H)=5 Hz, 2H Th-CH),7.02 (d, ³J_(H-H)=5 Hz, 2H Th-CH), 6.99 (d, ³J_(H-H)=5 Hz, 2H Th-CH),6.68 (d, ³J_(H-H)=5 Hz, 2H Th-CH), 2.81 (m, ³J_(H-H)=7 Hz, 4H Th-CH₂),1.70 (h, ³1_(H—H)=7 Hz, 4H, CH), 1.60 (m, 2H, CH), 1.40 (m, 4H, CH₂),1.34 (m, 14H, CH₂), 1.27 (m, 10H, CH₂), 1.15 (m, 4H, SiCH₂), 0.91 (m,8H, CH₃), 0.87 (m, 10H, CH₃). Absorbance: (CHCl₃) λ_(max)=645 nm,λ_(onset)=765 nm, ε=36500 cm⁻¹M⁻¹. (As Cast Film) λ_(max)=680 nm,λ_(onset)=875 nm.

The UV-VIS-NIR absorption spectrum of 104 in CHCl₃ solution and of afilm of 104 as-cast from CHCl₃ solution is shown in FIG. 4.

Example 5

Synthesis of4-(benzo[b]thiophen-2-yl)-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine(BzThPTBr): in a N₂ filled glove box a 20 mL glass tube was charged with4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 510 mg, 1.73 mmol), Na₂CO₃(1 g), Pd(PPh₃)₄ (0.050 g, 0.04 mmol), anhydrous THF (6 mL), and sealedwith a Teflon® cap. To this mixture was added de-gassed de-ionized water(5 mL) under Ar and the mixture stirred for 5 minutes.Benzothiophene-2-boronic acid (340 mg, 1.9 mmol) in anhydrous THF (6 mL)was then added to the reaction mixture which was subsequently purgedwith Ar for 5 minutes. The reaction mixture was heated to 90° C. andvigorously stirred for 16 hours. Upon cooling the reaction mixture waspoured into 500 mL of a 1:1 MeOH/H₂O solution and stirred for 20minutes. The precipitate that formed was collect by filtration andwashed with 500 mL of a 2:1 MeOH/H₂O solution and 100 mL of MeOH(product is slightly soluble in MeOH). The solid was dried under highvacuum for 48 hours. The product was collected as an orange solid.Recovered yield: 410 mg (68%). ¹H NMR (CDCl₃): δ 8.99 (s, 1H, PT-CH),8.74 (s, 1H, Th-CH), 7.94 (d, ³J_(H-H)=8 Hz, 1H Bz-CH), 7.91 (d,³J_(H-H)=8 Hz, 1H Bz-CH), 7.74 (t, ³J_(H-H)=8 Hz, 1H, Bz-CH), 7.71 (t,³J_(H-H)=8 Hz, 1H, Bz-CH). ¹³C{¹H} NMR (CDCl₃); 156.6, 148.4, 147.8 (s,quaternary), 145.7 (s, CH), 141.7, 141.1, 140.9 (s, quaternary), 130.3(s, CH), 126.7 (s, CH), 125.5 (s, CH), 125.1 (s, CH), 122.5 (s, CH),109.7 (s, quaternary). Anal. Calcd. for C₁₃H₆BrN₃S₂: C, 44.84; H, 1.74;N, 12.07. Found: C, 45.0; H, 1.46; N, 11.8%.

Synthesis of 105: In a N₂ filled glove box a 20 mL microwave tube wascharged with5,5′-Bis(trimethylstannyl)-3,3′-Di-2-ethylhexylsilylene-2,2′-bithiophene(Me₃Sn-SDT_(EH)-SnMe₃, 395 mg, 0.53 mmol),4-(benzo[b]thiophen-2-yl)-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine(BzThPTBr, 374 mg, 1.07 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene(15 mL), and sealed with a Teflon® cap. The reaction mixture was heatedto 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 60minutes, using a Biotage microwave reactor. Upon cooling, the residuewas passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500mL). All volatiles were removed in vacuo to give the crude product as apurple solid. The material was then loaded onto silica and purified byflash chromatography using a hexanes/CHCl₃ (5% Et₃N gradient. Afterfraction collection and solvent removal a purple solid was obtained. Thesolid was slurried in MeOH (300 mL), sonicated for 10 minutes, andfiltered. The solid was washed with copious amounts of MeOH and thendried under vacuum for 24 hours. The product was collected as purplesolid. Recovered yield: 350 mg (77%). ¹H NMR (CDCl₃): δ 8.77 (s, 2H,PT-CH), 8.64 (m, 2H Th—CH), 8.27 (t, 2H, SDT-CH), 7.88 (d, ³J_(H-H)=8Hz, 2H Bz-CH), 7.85 (d, ³J_(H-H)=8 Hz, 2H Bz-CH), 7.34 (m, ³J_(H-H)=8Hz, 4H, Bz-CH), 1.65 (h, ³J_(H-H)=6 Hz, 2H, CH), 1.43 (m, 4H, CH₂), 1.38(m, 4H, CH₂), 1.31 (m, 8H, CH₂), 1.19 (m, 4H, SiCH₂), 0.92 (t,³J_(H-H)=8 Hz, 6H, CH₃), 0.89 (t, ³J_(H-H)=8 Hz, 6H, CH₃). ³³C{¹H} NMR(CDCl₃): 154.17, 150.75, 148.09, 145.50, 145.49, 145.08, 141.74 (s,quaternary), 141.20 (s, CH), 139.65 (s, quaternary), 138.60 (s, CH),131.71 (m. SDT-CH, 128.82 (s, CH), 126.03 (s, quaternary), 125.04 (s,CH), 124.59 (s, quaternary), 122.39 (s, CH), 121.27 (s, CH), 36.13 (s,SiCH₂), 35.89 (s, CH), 29.10 (s, 2×CH₂), 23.11 (s, CH₂), 17.81 (s, CH₂),14.27 (s, CH₃), 10.93 (s, CH₃). Anal. Calcd. for C₅₀H₄₈N₆S₆Si: C, 62.99;H, 5.07; N, 8.81. Found: C, 62.8; H, 4.59; N, 8.82%. HRMS (EI) m/z,calcd for C₅₀H₄₈N₆S₆Si (M⁺): 952; found: 952. Absorbance: (CHCl₃)λ_(max)=594 nm, λ_(onset)=696 nm. (As Cast Film) λ_(max)=620, 664 nm,λ_(onset)=758 nm.

The UV-VIS-NIR absorption spectrum of 105 in CHCl₃ solution and of afilm of 105 as-cast from CHCl₃ solution is shown in FIG. 5.

Example 6

Synthesis of4-(benzofuran-2-yl)-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine(BzFuPTBr): In a N₂ filled glove box a 20 mL glass tube was charged with4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 300 mg, 1.01 mmol), Na₂CO₃(1 g), Pd(PPh₃)₄ (0.050 g, 0.04 mmol), anhydrous THF (6 mL), and sealedwith a Teflon® cap. To this mixture was added de-gassed de-ionized water(5 mL) under Ar and the mixture stirred for 5 minutes.Benzofuran-2-boronic acid (164 mg, 1.01 mmol) in anhydrous THF (6 mL)was then added to the reaction mixture which was subsequently purgedwith Ar for 5 minutes. The reaction mixture was heated to 90° C. andvigorously stirred for 16 hours. Upon cooling the reaction mixture waspoured into 500 mL of a 1:1 MeOH/H₂O solution and stirred for 20minutes. The precipitate that formed was collect by filtration andwashed with 500 mL of a 2:1 MeOH/H₂O solution and 100 mL of MeOH. Thecrude product was purified by flash chromatography eluting with ahexanes/CHCl₃ gradient. After fraction collection and solvent removalthe resulting orange solid was dried under high vacuum for 48 hours. Theproduct was collected as orange solid. Recovered yield: 205 mg (61%). ¹HNMR (CDCl₃): δ 8.88 (s, 1H, PT-CH), 8.44 (s, 1H, Th-CH), 7.78 (d,³J_(H-H)=8 Hz, 1H Bz-CH), 7.72 (d, ³J_(H-H)=8 Hz, 1H Bz-CH), 7.47 (dd,³J_(H-H)=8 Hz, 1H, Bz-CH), 7.34 (dd, ³J_(H-H)=8 Hz, 1H, Bz-CH). ¹³C{¹H}NMR (CDCl₃): 152.2, 148.1, 146.2. (s, quaternary), 144.4 (s, CH), 141.2,140.1, 138.3 (s, quaternary), 130.5 (s, CH), 125.5 (s, CH), 124.1 (s,CH), 123.8 (s, CH), 122.4 (s, CH), 110.2 (s, quaternary).

Synthesis of 106: In a N₂ filled glove box a 20 mL microwave tube wascharged with5,5′-Bis(trimethylstannyl)-3,3′-Di-2-ethylhexylsilylene-2,2′-bithiophene(Me₃Sn-SDT_(EH)-SnMe₃, 93 mg, 0.12 mmol),4-(benzofuran-2-yl)-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine (BzFuPTBr,83 mg, 0.25 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (15 mL), andsealed with a Teflon® cap. The reaction mixture was heated to 120° C.for 3 minutes, 140° C. for 3 minutes, and 175° C. for 60 minutes, usinga Biotage microwave reactor. Upon cooling, the residue was passedthrough a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). Allvolatiles were removed in vacuo to give the crude product as a purplesolid. The material was then loaded onto silica and purified by flashchromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fractioncollection and solvent removal a purple solid was obtained. Purificationby silica column chromatography was carried out twice. The solid wasslurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. Thesolid was washed with copious amounts of MeOH and then dried undervacuum for 24 hours. The product was collected as purple solid.Recovered yield: 59 mg (51%). ¹H NMR (CDCl₃); δ 8.97 (s, 2H, PT-CH),8.35 (m, 2H Fu-CH), 8.25 (m, 2H, SDT-CH), 7.75 (d, ³J_(H-H)=8 Hz, 2HBz-CH), 7.72 (d, ³J_(H-H)=8 Hz, 2H Bz-CH), 7.44 (dd. ³J_(H-H)=8 Hz, 2H,Bz-CH), 7.32 (dd, ³J_(H-H)=8 Hz, 2H, Bz-CH), 1.59 (h, ³J_(H-H)=7 Hz, 2H,CH), 1.40 (m, 4H, CH₂), 1.32 (m, 4H, CH₂), 1.26 (m, 8H, CH₂), 1.15 (m,4H, SiCH₂), 0.86 (M, 12H, CH₃). ¹³C{¹H} NMR (CDCl₃): 155.63, 154.36,151.23, 148.13, 145.63, 141.19 (s, quaternary), 140.16 (s, PT-CH),138.36 (s, quaternary), 138.60 (s, CH), 131.71 (s, SDT-CH), 128.89 (s,quaternary), 126.18, 123.56, 122.32 (s, Bz-CH), 121.77 (s, quaternary),113.53 (s, Fu-CH), 112.06 (s, Bz-CH), 36.07 (s, CH₂), 35.80 (s, CH),29.02 (s, CH₂), 28.97 (s, CH₂), 23.06 (s, CH₂), 17.76 (s, CH₂), 14.21(s, CH₃), 10.87 (s, CH₃). Anal. Calcd. for C₅₀H₄₈N₆O₂S₄Si: C, 65.18; H,5.25; N, 912. Found: C, 65.2; H, 5.22; N, 9.14%. HRMS (EI) m/z, calcdfor C₅₀H₄₈N₆O₂S₄Si (M⁺): 920; found: 920. Absorbance: (CHCl₃)λ_(max)=610 nm, λ_(onset)=695 nm. (As Cast Film) λ_(max)=625, 675 nm,λ_(onset)=760 nm.

The UV-VIS-NIR absorption spectrum of 106 in CHCl₃ solution and of afilm of 106 as-cast from CHCl₃ solution is Shown in FIG. 6.

Example 7

Synthesis of4-(benzo[d]thiazol-2-yl)-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine(BzTaPTBr): In a N₂ filled glove box a 20 mL glass tube was charged with4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 710 mg, 2.40 mmol),2-tributylstannylbenzothiazole (1.0 g, 2.36 mmol), Pd(PPh₃)₄ (0.050 g,0.04 mmol), anhydrous Toluene (15 mL), and sealed with a Teflon cap. Thereaction mixture was heated to 120° C. for 3 minutes, 140° C. for 3minutes, and 175° C. for 120 minutes, using a Biotage microwave reactor.Upon cooling, the residue was passed through a short silica plug elutingwith CHCl₃ (5% Et₃N) (500 mL). All volatiles were removed in vacuo togive the crude product as an orange solid. The material was then loadedonto silica and purified by flash chromatography using a hexanes/CHCl₃(5% Et₃N) gradient. After fraction collection and solvent removal anorange solid was obtained. The solid was slurried in MeOH (300 mL),sonicated for 10 minutes, and filtered. The solid was washed withcopious amounts of MeOH and then dried under vacuum for 24 hours. Theproduct was collected as orange solid. Recovered yield: 442 mg (53%). ¹HNMR (CDCl₃): δ 8.90 (s. 1H, PT-CH), 8.40 (d, ³J_(H-H)=9 Hz, 1H Bz-CH),8.03 (d, ³J_(H-H)=9 Hz, 1H Bz-CH), 7.59 (m, ³J_(H-H)=9 Hz, 1H, Bz-CH),7.53 (m, ³J_(H-H)=9 Hz, 1H, Bz-CH). ¹³C{¹H} NMR (CDCl₃): 158.2, 148.7,(s, quaternary), 146.5 (s, CH), 145.2, 141.7, 141.1, 140.9 (s,quaternary), 126.2 (s, CH), 125.3 (s, CH), 124.6 (s, CH), 122.8 (s, CH),111.4 (s, quaternary).

Synthesis of 107: In a N₂ filled glove box a 20 mL microwave tube wascharged with 5,5′-Bis(trimethylstannyl)-3,3′-Di 2ethylhexylsilylene-2,2′-bithiophene (Me₃Sn-SDT_(EH)-SnMe₃, 280 mg, 0.38mmol), benzo[d]thiazol-2-yl)-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine(BzTaPTBr, 263 mg, 0.75 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene(15 mL), and sealed with a Teflon cap. The reaction mixture was heatedto 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 120minutes, using a Biotage microwave reactor. Upon cooling, the residuewas passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500mL). All volatiles were removed in vacuo to give the crude product as apurple solid. The material was then loaded onto silica and purified byflash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. Afterfraction collection and solvent removal a purple solid was obtained.Purification by silica column chromatography was carried out twice. Thesolid was slurried in MeOH (300 mL), sonicated for 10 minutes, andfiltered. The solid was washed with copious amounts of MeOH and thendried under vacuum for 24 hours. The product was collected as purplesolid. Recovered yield: 220 mg (61%). ¹H NMR (CDCl₃): δ 9.07 (s, 2H,PT-CH), 8.41 (t, 2H, SDT-CH), 8.31 (d, ³J_(H-H)=9 Hz, 2H Bz-CH), 8.04(d, ³J_(H-H)=9 Hz, 2H Bz-CH), 7.56 (m, ₃J_(H-H)8 Hz, 2H, Bz-CH), 7.51(m, ³J_(H-H)=8 Hz, 2H, Bz-CH), 1.57 (m, 2H, CH), 1.4-1.1 (bm, 16H, CH₂),0.9-0.8 (m, 12H, CH₃). Anal. Calcd. for C₁₈H₄₆N₈S₆Si: C, 60.34; H, 4.85;N, 11.73. Found: C, 58.1; H, 4.51; N, 12.2%, HRMS (EI) m/z, calcd forC₅₀H₄₈N₆S₆Si (M⁺): 954; found: 954. Absorbance: (CHCl₃) λ_(max)=620 nm,λ_(onset)=725 nm. (As Cast Film) λ_(max)=620, 660 nm, λ_(onset)=775 nm.

The UV-VIS-NIR absorption spectrum of 107 in CHCl₃ solution and of afilm of 107 as-cast from CHCl₃ solution is shown in FIG. 7.

Example 8

Synthesis of5-(trimethylstannyl)-4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene(Me₃Sn-CDT_(EH)): A dry three-neck round bottom flask was equipped witha Schlenk adapter, dropping funnel, and rubber septum. Under argon,compound CDT_(EH) (2 g, 4.96 mmol) was dissolved in dry THF (200 mL) andcooled −78° C. using a dry ice/acetone cold bath. A solution oft-butyllithium (1.7 M pentane, 3.21 mL, 5.46 mmol) diluted with drypentane (30 mL) was then added dropwise over 20 minutes via a droppingfunnel. The dropping funnel was rinsed with dry pentane (30 mL) toensure all lithium reagent was transferred to the reaction vessel. Thereaction was stirred at −78° C. under argon for 2 hours. A solution oftrimethyltin chloride (1.5 g, 7.5 mmol) in dry pentane (30 mL) was thenadded dropwise over 5 minutes via a dropping funnel. The dropping funnelwas rinsed with dry pentane (30 mL) to ensure all tin reagent wastransferred to the reaction vessel. The reaction was stirred at −78° C.under argon for 1 hour and subsequently warmed to room temperature andstirred for a further 1 hour. The mixture was then poured intode-ionized water (300 mL) and the organic phase extracted with hexanes(3×100 mL). The organic phases were collected and washed with de-ionizedwater (5×100 mL), dried over magnesium sulphate, filtered, andconcentrated to give the product as yellow oil. Yield 2.65 g (95%). ¹HNMR (500 MHz, CD₂Cl₂): δ 7.11 (m, 1H), 7.00 (m, 1H), 6.95 (m, 1H), 1.89(m, 4H, C-CH₂), 1.1-0.8 (m, 18H, alkyl), 0.75 (m, 6H, alkyl), 0.60 (m,8H, alkyl), 0.36 (s, d, 9H, ²J_(H-Sn)=57 Hz, Sn—CH₃).

Synthesis of4-4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-′]dithiophene-7-bromo-[1,2,5]thiadiazolo[3,4-c]pyridine(CDTPTBr): In a N₂ filled glove box a 20 mL glass tube was charged with4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 520 mg, 1.76 mmol),5-(trimethylstannyl)-4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene(Me₃Sn-CDT_(EH), 985 mg, 1.74 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol),anhydrous xylenes (15 mL), and sealed with a Teflon® cap. The reactionmixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and175° C. for 60 minutes, using a Biotage microwave reactor. Upon cooling,the residue was passed through a short silica plug eluting with CHCl₃(5% Et₃N) (500 mL). All volatiles were removed in vacuo to give thecrude product as a red-purple oil. The material was then loaded ontosilica and purified by flash chromatography using a hexanes/CH₂Cl₂gradient. The second fraction was collected and all solvent was removedin vacuo to give the product as a deep-red oil. Recovered yield: 910 mg(85%). ¹H NMR (CD₂Cl₂): δ 8.62 (m, 1H, Th-CH), 8.56 (s, 1H, PT-CH), 7.34(d, ³J_(H-H)=8 Hz, 1H Th—CH), 7.03 (m, ³J_(H-H)=6 Hz, 1H Th-CH), 2.04(m, 2H, C-CH₂), 1.95 (m, 2H, C-CH₂), 1.00 (m, 8H, alkyl), 0.96 (m, 8H,alkyl), 0.73 (m, 4H, alkyl), 0.69 (m, 2H, alkyl), 0.61 (m, 8H, alkyl).

Synthesis of 108: In a N₂ filled glove box a 5 mL microwave tube wascharged with Me₃Sn-BDT_(EH)-SnMe₃ (270 mg, 0.35 mmol), CDTPTBr (430 mg,0.70 mmol), Pd(PRh₃)₄ (0.025 g, 0.02 mmol), xylenes (4 mL), and sealedwith a Teflon® cap. The reaction mixture was heated to 120° C. for 3minutes, 140° C. for 3 minutes, and 175° C. for 180 minutes, using aBiotage microwave reactor. Upon cooling, the residue was passed througha short silica plug eluting with CHCl₃. All volatiles were removed invacuo to give the crude product as a purple solid. The material was thenloaded onto silica and purified by flash chromatography using ahexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solventremoval a purple solid was obtained. The solid was slurried in MeOH (300mL), sonicated for 10 minutes, and filtered. The solid was washed withcopious amounts of MeOH and then dried under vacuum for 24 hours. Theproduct was collected as purple solid. Recovered yield: 430 mg (81%). ¹HNMR (CDCl₃): δ 8.92 (s, 2H, PT-CH), 8.76 (m, 2H, Th-CH), 8.66 (m, 2H,Th-CH), 7.32 (d, ³J_(H-H)=5 Hz, 2H Th-CH), 7.02 (m, ³J_(H-H)=5 Hz, 2HTh-CH), 4.36 (m, 4H, OCH), 2.09 (m, 4h, CH₂), 1.98 (m, 6H, CH₂), 1.85(m, 2H, CH₂), 1.79 (m, 2H, CH₂), 1.72 (m, 2H, CH₂), 1.62 (m, 2H, CH₂),1.51 (m, 8H, CH₂), 1.14 (m, 6H, CH₃), 1.00 (m, 36H, CH₂, CH ₃), 0.75 (m,12H, CH₃), 0.62 (m, 18H, CH₃). ¹³C{¹H} NMR (CDCl₃): 160.41, 159.75,155.15, 148.10, 147.79, 144.80, 143.99 (s, quaternary), 142.73 (s,PT-CH), 141.39, 136.95, 136.75, 133.30, 129.47 (s, quaternary), 127.88,127.39, 122.53, 121.97 (s CH), 119.22 (s, quaternary), 76.27 (s, OCH₂),53.88, 43.35, 43.12, 40.81, 35.28, 35.25, 32.23, 30.68, 29.37, 28.66,28.52, 27.49, 27.40, 24.02, 23.27, 22.78, 14.31, 14.07, 14.02, 11.52,10.78, 10.63. Anal. Calcd. for C₈₆H₁₁₂N₆O₂S₈: C, 68.03; H, 7.43; N,5.53. Found: C, 67.9; H, 7.22; N, 5.63%. Absorbance: (CHCl₃) λ_(max)=635nm, λ_(onset)=715 nm. (As Cast Film) λ_(max)=640, 670 nm, λ_(onset)=790nm.

The UV-VIS-NIR absorption spectrum of 108 in CHCl₃ solution and of afilm of 108 as-cast from CHCl₃ solution is shown in FIG. 8.

Example 9

Synthesis of5-(trimethylstannyl)-4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene(Me₃Sn-CDT_(EH)): A dry three-neck round bottom flask was equipped witha Schlenk adapter, dropping funnel, and rubber septum. Under argon,compound CDT_(EH) (2 g, 4.96 mmol) was dissolved in dry THF (200 mL) andcooled −78° C. using a dry ice/acetone cold bath. A solution oft-butyllithium (1.7 M pentane, 3.21 mL, 5.46 mmol) diluted with drypentane (30 mL) was then added dropwise over 20 minutes via a droppingfunnel. The dropping funnel was rinsed with dry pentane (30 mL) toensure all lithium reagent was transferred to the reaction vessel. Thereaction was stirred at −78° C. under argon for 2 hours. A solution oftrimethyltin chloride (1.5 g, 7.5 mmol) in dry pentane (30 mL) was thenadded dropwise over 5 minutes via a dropping funnel. The dropping funnelwas rinsed with dry pentane (30 mL) to ensure all tin reagent wastransferred to the reaction vessel. The reaction was stirred at −78° C.under argon for 1 hour and subsequently warmed to room temperature andstirred for a further 1 hour. The mixture was then poured intode-ionized water (300 mL) and the organic phase extracted with hexanes(3×100 mL). The organic phases were collected and washed with de-ionizedwater (5×100 mL), dried over magnesium sulphate, filtered, andconcentrated to give the product as yellow oil. Yield 2.65 g (95%). ¹HNMR (500 MHz, CD₂Cl₂): δ 7.11 (m, 1H), 7.00 (m, 1H), 6.95 (m, 1H), 1.89(m, 4H, C-CH₂), 1.1-0.8 (m 18H, alkyl), 0.75 (m, 6H, alkyl), 0.60 (m,8H, alkyl), 0.36 (s, d, 9H, ²J_(H—Sn)=57 Hz, Sn—CH₃).

Synthesis of CDT_(EH)PhNPh₂: In a N₂ filled glove box a 20 mL glass tubewas charged with 4-bromotriphenylamine (404 mg, 1.25 mmol),(Me₃Sn-CDT_(EH), 700 mg, 1.24 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol),anhydrous xylenes (15 mL), and sealed with a Teflon cap. The reactionmixture was heated to 120° C. for 3 minutes, 140° C. for 3 minutes, and175° C. for 60 minutes, using a Biotage microwave reactor. Upon cooling,the residue was passed through a short silica plug eluting with CHCl₃(500 mL). An volatiles were removed in vacuo to give the crude productas an orange oil. The material was then loaded onto silica and purifiedby flash chromatography using a hexanes/CH₂Cl₂ gradient. The secondfraction was collected and all solvent was removed in vacuo to give theproduct as an orange oil. The product was dried under high vacuum for 24hours. Recovered yield: 658 mg (82%). ¹H NMR (CD₂Cl₂): δ 7.47 (m, 2H),7.27 (m, 4H), 7.15 (m, 1H, CDT), 7.14 (m, 1H, CDT), 7.11 (m, 4H), 7.05(m, 4H), 6.97 (m, 1H, CDT), 1.91 (m, 4H), 1.01 (m, 10H), 0.95 (m, 4H),0.93 (m, 2H), 0.76 (m, 3H), 0.73 (m, 3H), 0.68 (m, 2H), 0.63 (m, 3H),0.61 (m, 3H), Anal. Calcd. for C₄₃H₅₁N₁S₂: C, 79.95; H, 7.96; N, 2.17.Found: C, 79.9; H, 7.99; N, 2.50%.

Synthesis of Me₃Sn-CDT_(EH)PhNPh₂: A dry three-neck round bottom flaskwas equipped with a Schlenk adapter, dropping funnel, and rubber septum.Under argon, compound CDT_(EH)PhNPh₂ (630 mg, 0.98 mmol) was dissolvedin dry THF (100 mL) and cooled −78° C. using a dry ice/acetone coldbath. A solution of t-butyllithium (1.7 M pentane, 0.69 mL, 1.17 mmol)diluted with dry pentane (30 mL) was then added dropwise over 20 minutesvia a dropping funnel. The dropping funnel was rinsed with dry pentane(30 mL) to ensure all lithium reagent was transferred to the reactionvessel. The reaction was stirred at −78° C. under argon for 2 hours. Asolution of trimethyltin chloride (293 mg, 1.47 mmol) in dry pentane (30mL) was then added dropwise over 5 minutes via a dropping funnel. Thedropping funnel was rinsed with dry pentane (30 mL) to ensure all tinreagent was transferred to the reaction vessel. The reaction was stirredat −78° C. under argon for 1 hour and subsequently warmed to roomtemperature and stirred for a further 2 hours. The mixture was thenpoured into de-ionized water (300 mL) and the organic phase extractedwith diethyl ether (3×200 mL). The organic phases were collected andwashed with de-ionized water (5×200 mL), dried over magnesium sulphate,filtered, and concentrated to give the product as red oil. The productwas dried under high vacuum for 24 hours. Yield 780 mg (95%). ¹H NMR(CD₂Cl₂): δ 7.46 (m, 2H), 7.27 (m, 4H), 7.13 (m, 1H, CDT), 7.11 (m, 4H),7.04 (m, 4H), 7.01 (m, 1H, CDT), 1.88 (m, 4H), 0.99 (m, 14H), 0.88 (m,4H), 0.74 (m, 6H), 0.64 (m, 3H), 0.60 (m, 3H), 0.37 (m, 9H).

Synthesis of BrPT-CDT_(EH)PhNPh₂: In a filled glove box a 5 mL glasstube was charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 140mg, 0.47 mmol), Me₃Sn-CDT_(EH)PhNPh₂ (385 mg, 0.48 mmol), Pd(PPh₃)₄(0.025 g, 0.02 mmol), anhydrous xylenes (4 mL), and sealed with a Tefloncap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C.for 3 minutes, and 175° C. for 60 minutes, using a Biotage microwavereactor. Upon cooling, the residue was passed through a short silicaplug eluting with CHCl₃ (5% Et₃N) (500 mL). An volatiles were removed invacuo to give the crude product as a dark solid. The material was thenloaded onto silica and purified by flash chromatography using ahexanes/CHCl₃ (5% Et₃N) gradient. The product eluted as a large bluefraction at 60:40 hexanes/CHCl₃ (5% Et₃N). The fractions were collectedand all solvent was removed in vacuo to give the product as a purplefilm. The product was then dissolved in a minimal amount of CHCl₃ andstirred for 5 minutes. All solvent was then removed and the productdried under high vacuum for 24 hours. The product was obtained as apurple solid. Recovered yield: 290 mg (71%). ¹H NMR (CDCl₃): δ 8.59 (s,1H, PT), 8.57 (m. J=6 Hz, 1H CDT), 7.49 (m, ³J_(H-H)=5 Hz, 2H), 7.29 (m,³J_(H-H)=8 Hz, 4H), 7.15 (m, 5H), 7.08 (m, ³J_(H-H)=8 Hz, 4H), 2.05 (m,2H), 1.95 (m, 2H), 0.99 (m, 16H), 0.81 (m, 2H), 0.73 (m, 3H), 0.64 (m,9H).

Synthesis of 109: In a N₂ filled glove box a 5 mL microwave tube wascharged with Me₃Sn-BDT_(C6)-SnMe₃ (100 mg, 0.14 mmol),BrPT-CDT_(EH)PhNPh₂ (240 mg, 0.28 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol),xylenes (4 mL), and sealed with a Teflon cap. The reaction mixture washeated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for60 minutes, using a Biotage microwave reactor. Upon cooling, the residuewas passed through a short silica plug eluting with CHCl₃ (5% Et₃N). Allvolatiles were removed in vacua to give the crude product as a darksolid. The material was then loaded onto silica and purified by flashchromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fractioncollection and solvent removal a dark purple film was obtained. The filmwas slurried in MeOH (300 mL), sonicated for 10 minutes, and filtered.The solid was washed with copious amounts of MeOH and then dried undervacuum for 24 hours. The product was collected as a dark metallic flakeysolid was obtained. Recovered yield: 250 mg (92%). ¹H NMR (CD₂Cl₂): δ8.86 (s, 2H, BDT), 8.73 (s, 2H, PT), 8.71 (m, J=6 Hz, 2H, CDT), 7.52 (m,2H, Ph), 7.50 (m, 2H, Ph), 7.23 (m, ³J_(H-H)=8 Hz, 8H, Ph), 7.22 (br s,2H, CDT), 7.13 (m, ³J_(H-H)=8 Hz, 8H, Ph), 7.07 (m, 8H, Ph), 4.46 (t,³J_(H-H)=6 Hz, 4H, OCH₂), 2.09 (m, 4H), 2.01 (m, 8H), 1.73 (m, 4H), 1.48(m, 8H), 1.08-0.94 (m, 34H), 0.84 (m, 6H), 0.74 (m, 6H), 0.66 (m, 18H).¹³C{¹H} NMR (CD₂Cl₂): 162.33, 159.95, 155.67, 148.66, 148.30, 148.03,147.99, 147.78, 145.15, 144.89 (quaternary), 143.26 (BDT-CH), 142.14,137.55, 136.13, 133.83, 130.25 (quaternary), 129.92 (Ph-CH), 129.51(quaternary), 1:28.52 (t, CDT-CH), 126.75, 125.23, 124.05, 123.87(Ph-CH), 122.18 (PT-CH), 119.49 (quaternary), 118.36 (t, CDT-CH), 74.88(OCH₂), 54.85 (CDT-bridge), 43.71, 43.64 (d, 2-ethylhexyl-CH), 36.00,34.82, 34.77, 34.75, 32.37, 31.22, 29.27, 29.10, 28.15, 28.05, 26.50,23.42, 23.40 (CH₂), 14.53, 14.42, 14.37, 11.15, 11.04 (CH₃). Anal Calcd.for C₁₁₈H₁₃₄N₈O₂S₈: C, 72.57; H, 6.92; N, 5.74. Found: C, 72.8; H, 6.55;N, 5.24%. Absorbance: (CHCl₃) λ_(max)=675 nm, λ_(onset)=766 nm, ε=56 000cm⁻¹M⁻¹. (As Cast Film) λ_(max)=705, 665 nm, λ_(onset)=820 nm.

The UV-VIS-NIR absorption spectrum of 109 in CHCl₃ solution and of afilm of 109 as-cast from CHCl₃ solution is shown in FIG. 9.

Example 10

Synthesis of 110: In a N₂ filled glove box a 5 mL microwave tube wascharged with Me₂Sn-BDT_(EH)-SnMe₃ (300 mg, 0.39 mmol), HexTPTBr (326 mg,0.85 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), xylenes (4 mL), and sealedwith a Teflon cap. The reaction mixture was heated to 120° C. for 3minutes, 140° C. for 3 minutes, and 175° C. for 60 minutes, using aBiotage microwave reactor. Upon cooling, the residue was passed througha short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatileswere removed in vacuo to give the crude product as a purple solid. Thematerial was then loaded onto silica and purified by flashchromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. After fractioncollection and solvent removal a purple solid was obtained. Purificationby silica column chromatography was carried out twice to ensure completeremoval of all trace impurities and by-products. The solid was slurriedin MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid waswashed with copious amounts of MeOH and then dried under vacuum for 24hours. The product was collected as a purple solid. Recovered yield: 390mg (96%). ¹H NMR (CDCl₃): δ 8.45 (s, 2H, PT-CH), 8.31 (s, 2H, BDT-CH),8.19 (d, ³J_(H-H)=5 Hz, 2H Th-CH), 6.66 (d, ³J_(H-H)=5 Hz, 2H Th-CH),4.22 (br m, 4H, OCH), 2.76 (m, 4H, Th-CH₂), 1.86 (br m, 4H, CH₂),1.79-1.60 (m, 10H, CH₂), 1.54 (br m, 8H, CH₂), 1.39 (br m, 4H, CH₂),1.33 (br m, 8H, CH₂), 1.16 (t, ³J_(H-H)=8 Hz, 6H, CH₃), 1.06 (t,³J_(H-H)=5 Hz, 6H, CH₃), 0.92 (m, ³J_(H-H)=8 Hz, 6H, CH₃). ¹³C{¹H} NMR(CDCl₃): 154.37, 152.45, 147.74, 146.25, 144.27, 142.84 (s, quaternary),141.48 (CH), 138.81, 135.52, 132.86 (s, quaternary), 132.11 (CH), 128.70(s, quaternary), 126.10, 122.13 (CH), 119.28 (s, quaternary). Anal.Calcd. for C₅₆H₆₈N₆O₂S₆: C, 64.08; H, 6.53; N, 8.01. Found: C, 64.0; H,6.35; N, 8.10%. Absorbance: (CHCl₃) λ_(max)=560 nm, λ_(onset)=670 nm.(As Cast Film) λ_(max)=590, 630 nm, λ_(onset)=725 nm.

The UV-VIS-NIR absorption spectrum of 110 in CHCl₃ solution and of afilm of 110 as-cast from CHCl₃ solution is shown in FIG. 10.

Example 11

Synthesis of 111: In a N₂ filled glove box a 5 mL microwave tube wascharged with Me₃Sn-BDT_(EH)-SnMe₃ (191 mg, 0.27 mmol), HexTTPTBr (230mg, 0.50 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol), xylenes (4 mL), andsealed with a Teflon cap. The reaction mixture was heated to 120° C. for3 minutes, 140° C. for 3 minutes, and 175° C. for 120 minutes, using aBiotage microwave reactor. Upon cooling, the residue was transferred toa 500 mL round bottom flask using CHCl₃ and all volatiles removed invacuo to give the crude product as a purple solid. The solid wasslurried in MeOH (300 mL), sonicated for 10 minutes, and filtered. Thesolid was washed with copious amounts of MeOH, Acetone, iPrOH, hexanesusing a soxhelt apparatus and then dried under vacuum for 24 hours. Theproduct was collected as a purple solid. Recovered yield: 170 mg (57%).Compound 111 exhibits very low solubility in organic solvents (<5 mg/mLin CHCl₃) and minimal movement on silica-gel.

The UV-VIS-NIR absorption spectrum of 111 in CHCl₃ solution and of afilm of 111 as-cast from CHCl₃ solution is shown in FIG. 11.

Example 12

Synthesis of 112: In a filled glove box a 20 mL microwave tube wascharged with5,5′-Bis(trimethylstannyl)-3,3′-di-2-hexylsilylene-2,2′-bithiophene(Me₃Sn-SDT_(Hex)-SnMe₃, 500 mg, 0.73 mmol),7-bromo-4-(5-hexylthiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine(HexThPTBr, 560 mg, 1.46 Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (15mL), and sealed with a Teflon® cap. The reaction mixture was heated to120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for 120minutes, using a Biotage microwave reactor. Upon cooling, the residuewas passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500mL). All volatiles were removed in vacuo to give the crude product as apurple solid. The material was then loaded onto silica and purified byflash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. Afterfraction collection and solvent removal a purple solid was obtained.Purification by silica column chromatography was carried out twice. Thesolid was slurried in MeOH (300 mL), sonicated for 10 minutes, andfiltered. The solid was washed with copious amounts of MeOH and thendried under vacuum for 24 hours. The product was collected as purplesolid. Recovered yield: 480 mg (69%). ¹H NMR (CDCl₃): δ 8.60 (s, 2H,PT-CH), 8.36 (d, ³J_(H-H)=5 Hz, 2H, Th-CH), 8.15 (t, 2H, SDT-CH), 6.90(d, ³J_(H-H)=5 Hz, 2H, Th-CH), 2.90 (t, ³J_(H-H)=7 Hz, 4H Th-CH₂), 1.79(tt, ³J_(H-H)=7 Hz, 4H, CH₂), 1.56 (m, 4H, CH), 1.44 (br m, 8H, CH₂),1.36 (m, 8H, CH₂), 1.32 (m, 8H, CH₂), 1.10 (m, 4H, SiCH₂), 0.92 (m, 6H,CH₃), 0.88 (m, 6H, CH₃). ¹³C{¹H} NMR (CDCl₃): 154.25, 152.97, 150.47,147.69, 145.35, 143.97 (s, quaternary), 139.96 (s, CH), 139.10, 138.65(s, quaternary), 131.96 (s, CH), 130.63 (s, CH), 126.30 (s, CH), 119.99(s, quaternary), 32.99 (s, CH₂), 31.57 (s, CH₂), 31.51 (s, CH₂), 30.39(s, CH₂), 30.56 (s, CH₂), 28.81 (s, CH₂), 24.29 (s, CH₂), 26.61 (s,CH₂), 22.57 (s, CH₂), 14.11 (s, CH₂), 14.07 (s, CH₃), 11.99 (s, CH₃).Anal, Calcd, for C₅₀H₆₀N₆S₆Si: C, 62.20; H, 6.26; N, 8.70. Found: C,62.2; H, 6.16; N, 8.67%. Absorbance: (CHCl₃) λ_(max)=600 nm,λ_(onset)=715 nm. (As Cast Film) λ_(max)=625, 675 nm, λ_(onset)=795 nm.

The UV-VIS-NIR absorption spectrum of 112 in CHCl₃ solution and of afilm of 112 as-cast from CHCl₃ solution is shown in FIG. 12.

Example 13

Synthesis of 113: In a N₂ filled glove box a 20 mL microwave tube wascharged with5,5′-Bis(trimethylstannyl)-3,3′-dihexylsilylene-2,2′-bithiophene(Me₃Sn-SDT_(HEX)-SnMe₃, 394 mg, 0.57 mmol),7-bromo-4-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine(HexThThPTBr, 530 mg, 1.14 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol),toluene (15 mL), and sealed with a Teflon cap. The reaction mixture washeated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for120 minutes, using a Biotage microwave reactor. Upon cooling, theresidue was passed through a short silica plug eluting with CHCl₃ (5%Et₃N) (500 mL). All volatiles were removed in vacuo to give the crudeproduct as a purple solid. The material was then loaded onto silica andpurified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N)gradient. After fraction collection and solvent removal a purple solidwas obtained. Purification by silica column chromatography was carriedout twice. The solid was slurried in MeOH (300 mL), sonicated for 10minutes, and filtered. The solid was washed with copious amounts of MeOHand then dried under vacuum for 24 hours. The product was collected aspurple solid. Recovered yield: 520 mg (80%). ¹H NMR (CDCl₃): δ 8.64 (s,2H, PT-CH), 8.44 (m, 2H, Th-CH), 8.11 (m, 2H, SDT-CH), 7.16 (d,³J_(H-H)=5 Hz, 2H Th-CH), 7.15 (d, ³J_(H-H)=5 Hz, 2 Hz, Th-CH), 6.72 (m,2H, Th—CH), 2.81 (t, ³J_(H-H)=7 Hz, 4H Th-CH₂), 1.73 (tt, ³J_(H-H)=6 Hz,4H, CH₂), 1.57 (m, 4H, CH₂), 1.41 (br m, 8, CH₂), 1.33 (br m, 16H, CH₂),1.10 (m, 4H, CH₂), 0.93 (m, 6H, CH₃), 0.88 (m 6H, CH₃). Absorbance:(CHCl₃) λ_(max)=630 nm, λ_(onset)=735 nm. (As Cast Film) λ_(max)=660,715 nm, λ_(onset)=800 nm.

The LTV-VIS NIR absorption spectrum of 113 in CHCl₃ solution and of afilm of 113 as-cast from CHCl₃ solution is shown in FIG. 13.

Example 14

Synthesis of 114: In a N₂ filled glove box a 5 mL microwave tube wascharged with5,5′-Bis(trimethylstannyl)-3,3′-di-2-dodecilsilylene-2,2′-bithiophene(Me₃Sn-SDT_(C12)-SnMe₃, 370 mg, 0.43 mmol),7-bromo-4-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[3,4-c]pyridine(HexThThPTBr, 400 mg, 0.86 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol),toluene (4 mL), and sealed with a Teflon cap. The reaction mixture washeated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for60 minutes, using a Biotage microwave reactor. Upon cooling, the residuewas passed through a short silica plug eluting with CHCl₃ (5% Et₃N) (500mL). All volatiles were removed in vacuo to give the crude product as apurple solid. The material was then loaded onto silica and purified byflash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. Afterfraction collection and solvent removal a purple solid was obtained.Purification by silica column chromatography was carried out twice. Thesolid was slurried in MeOH (300 mL), sonicated for 10 minutes, andfiltered. The solid was washed with copious amounts of MeOH and thendried under vacuum for 24 hours. The product was collected as purplesolid. Recovered yield: 500 mg (89%). ¹H NMR (CDCl₃): δ 8.57 (s, 2H,PT-CH), 8.36 (d, ³J_(H-H)=5 Hz, 2H, Th-CH), 8.09 (m, 2H, SDT-CH), 7.13(d, ³J_(H-H)=5 Hz, 4H Th-CH), 6.71 (m, 2H, Th-CH), 2.81 (m, 4H Th—CH₂),1.71 (m, 4H, CH₂), 1.59 (m, 4H, CH₂), 1.43 (br m, 8H, CH₂), 1.35 (m,12H, CH₂), 1.24 (br m, 28H, CH₂), 1.11 (m, 4H, CH₂), 0.93 (m, 6H, CH₃),0.85 (m, 6H, CH₃). Anal. Calcd. for C₇₀H₈₈N₆S₈Si: C, 64.77; H, 6.83; N,6.47. Found: C, 64.5; H, 6.90; N, 6.56%. Absorbance: (CHCl₃) λ_(max)=630nm, λ_(onset)=750 nm. (As Cast Film) λ_(max)=655, 715 nm. λ_(onset)=825nm.

The UV-VIS-NIR absorption spectrum of 114 in CHCl₃ solution and of afilm of 114 as-cast from CHCl₃ solution is shown in FIG. 14.

Example 15

Synthesis of 11.5 (G9-C): In a N₂ filled glove box a 20 mL microwavetube was charged with4,4-bis(2-ethylhexyl)-2,6-bis(trimethylstannyl)-4H-cyclopenta[2,1-b:3,4-b′]dithiophene(Me₃Sn-CDT_(EH)-SnME₃, 520 mg, 0.71 mmol),7-bromo-4-(5-(5-hexylthiophen-2-yl)thiophen-2-yl)-[1,2,5]thiadiazolo[34-c]pyridine(HexThThPTBr, 637 mg, 1.37 mmol), Pd(PPh₃)₄ (0.025 g, 0.02 mmol),toluene (15 mL), and sealed with a Teflon cap. The reaction mixture washeated to 120° C. for 3 minutes, 140° C. for 3 minutes, and 175° C. for120 minutes, using a Biotage microwave reactor. Upon cooling, theresidue was passed through a short silica plug eluting with CHCl₃ (5%Et₃N) (500 mL). All volatiles were removed in vacuo to give the crudeproduct as a purple solid. The material was then loaded onto silica andpurified by flash chromatography using a hexanes/CHCl₃ (5% Et₃N)gradient. After fraction collection and solvent removal a purple solidwas obtained. Purification by silica column chromatography was carriedour twice. The solid was slurried in MeOH (300 sonicated for 10 minutes,and filtered. The solid was washed with copious amounts of MeOH and thendried under vacuum for 24 hours. The product was collected as purplesolid. Recovered yield: 710 mg (85%). ¹H NMR (CDCl₃): δ 8.83 (s, 2H,PT-CH), 8.58 (d, ³J_(H-H)=5 Hz, 2H, Th-CH), 8.10 (t, 2H, SDT-CH), 7.25(d, ³J_(H-H)=5 Hz, 2 Hz, Th-CH), 7.19 (d, ³J_(H-H)=5 Hz, 2H Th-CH), 6.76(m, 2H, Th-CH), 2.84 (m, 4H Th-CH₂), 2.08 (m, 4H, CH₂), 1.72 (tt,³J_(H-H)=6 Hz, 4H, CH₂), 1.42 (m, 4H, CH), 1.35 (m, 8H, CH₂), 1.05-1.00(br m, 14H, CH₂), 0.92 (m, 6H, CH₂), 0.84 (m, 4H, CH₂), 0.66 (m, 12H,CH₃). Absorbance: (CHCl₃) λ_(max)=655 nm, X_(onset)=765 nm. (As CastFilm) λ_(max)=680, 740 nm, λ_(max)=845 nm.

The UV-VIS-NIR absorption spectrum of 115 in CHCl₃ solution and of afilm of 115 as-cast from CHCl₃ solution is shown in FIG. 15.

Example 16

Synthesis of BrPT-SDT-PTBr: In a N₂ filled glove box a 20 mL glass tubewas charged with 4,7-dibromo-pyridal[2,1,3]thiadiazole (PTBr₂, 1.27 g,4.31 mmol),5,5′-Bis(trimethylstannyl)-3,3′-di-2-ethylhexylsilylene-2,2′-bithiophene(Me₃Sn-SDT_(EH)-SnMe₃, 800 mg, 1.07 mmol), Pd(PPh₃)₄ (0.025 g, 0.02mmol), toluene (15 mL), and sealed with a Teflon cap. The reactionmixture was heated to 100° C. for 15 hours, during which a color changefrom yellow to purple was observed. Upon cooling, the residue was passedthrough a short silica plug eluting with CHCl₃ (5% Et₃N) (500 mL). Allvolatiles were removed in vacuo to give the crude product as a darksticky solid. The material was then loaded onto silica and purified byflash chromatography using a hexanes/CHCl₃ (5% Et₃N) gradient. Theproduct eluted as a purple solution at 80% CHCl₃ (5% Et₃N). Afterfraction collection and solvent removal, the solid product was slurriedin MeOH (300 mL), sonicated for 10 minutes, and filtered. The solid waswashed with copious amounts of MeOH and then dried under vacuum for 24hours. The product was collected as green metallic coloured powder.Recovered yield: 550 mg (60%). ¹H NMR (CDCl₃): δ 8.76 (s, 214, PT-CH),8.66 (s, 2H, SDT-CH), 1.52 (m, 2H, CH), 1.39 (m, 4H, CH₂), 1.31 (m, 4H,CH₂), 1.16 (m, 8H, CH₂), 1.06 (m, 4H, CH₂), 0.85 (m, 12H, CH₃). ¹³C{¹H}NMR (CDCl₃): 156.38, 153.85, 147.98, 147.66, 147.49 (s, quaternary),146.03 (s, CH), 143.94 (s, quaternary), 135.99 (s, CH), 107.64 (s,quaternary), 36.02 (s, CH), 35.76 (s, CH₂), 22.97 (s, CH₂), 22.93 (s,CH₂), 20.92 (s, CH₂), 17.64 (s, CH₂), 14.15 (s, CH₃). 10.80 (s, CH₃).

Synthesis of 116: In a N₂ filled glove box a 5 mL microwave tube wascharged with BrPT-SDT-PTBr (420 mg, 0.50 mmol),5′-hexyl-2,2′-bithiophene 5 trimethylstannane (450 mg, 1.09 mmol),Pd(PPh₃)₄ (0.025 g, 0.02 mmol), toluene (4 mL), and sealed with a Tefloncap. The reaction mixture was heated to 120° C. for 3 minutes, 140° C.for 3 minutes, and 175° C. for 120 minutes, using a Biotage microwavereactor. Upon cooling, the residue was passed through a short silicaplug eluting with CHCl₃ (5% Et₃N) (500 mL). All volatiles were removedin vacuo to give the crude product as a purple solid. The material wasthen loaded onto silica and purified by flash chromatography using ahexanes/CHCl₃ (5% Et₃N) gradient. After fraction collection and solventremoval a purple solid was obtained. Purification by silica columnchromatography was carried out twice. The solid was slurried in MeOH(300 mL), sonicated for 10 minutes, and filtered. The solid was washedwith copious amounts of MeOH and then dried under vacuum for 24 hours.The product was collected as purple solid. Recovered yield: 475 mg(81%). ¹H NMR (CDCl₃): δ 8.72 (t, 2H, SUE-CH), 8.70 (s, 2H, PT-CH), 7.95(d, ³J_(H-H)=5 Hz, 2H, Th-CH), 7.16 (d, ³J_(H-H)=5 Hz, 2H, Th-CH), 7.11(d, ³J_(H-H)=5 Hz, 2H, Th-CH), 6.73 (d, ³J_(H-H)=5 Hz, 2H, Th-CH), 2.83(t, ³J_(H-H)=8 Hz, 4H Th-CH₂), 1.72 (h, ³J_(H-H)=6 Hz, 4H, CH₂), 1.62(m, 2H, CH), 1.41 (m, 8H, CH₂), 1.35 (m, 12H, CH₂), 1.28 (m, 8H, CH₂),1.18 (m, 4H, SiCH₂), 0.92-0.83 (m, 18H, CH₃). ¹³C{¹H} NMR (CDCl₃):154.56, 153.65, 147.98, 147.43, 146.27, 145.76, 144.77, 140.43 (s,quaternary), 139.63 (s, PT-CH), 135.19, 134.85 (s, quaternary), 134.44(s, SDT-CH), 128.42 (s, Th-CH), 125.01 (s, Th-CH), 123.99 (s, Th-CH),123.85 (s, Th-CH), 119.59 (s, quaternary), 36.10 (s, CH), 35.86 (s,CH₂), 31.57 (s, Si—CH₂), 30.26 (s, Th-CH₂), 29.08 (s, CH₂), 29.01 (s,CH₂), 28.80 (s, CH₂), 23.08 (s, CH₂), 22.59 (s, CH₂), 17.73 (s, CH₂),14.26 (s, CH₃), 14.09 (s, CH₃), 10.88 (s, CH₃). Absorbance: (CHCl₃)λ_(max)=655 nm, λ_(onset)=715 nm, ε=37400 cm⁻¹ M⁻¹. (As Cast Film)λ_(max)=655, 725 nm, λ_(onset)=815 nm.

The UV-VIS-NIR absorption spectrum of 116 in CHCl₃ solution and of afilm of 116 as-cast from CHCl₃ solution is shown in FIG. 16.

Example 17 Determination of HOMO-LUMO Values

Electrochemistry: All electrochemical measurements were performed usingCHI instrument model 730B in a standard three-electrode, one compartmentconfiguration equipped with Ag/AgCl electrode, Pt wire and Glassy carbonelectrode (dia. 3 mm), as the pseudo reference, counter electrode andworking electrode respectively. Glassy carbon electrodes were polishedwith alumina. The cyclic voltammetry (CV) experiments were performed inanhydrous dichloromethane (DCM) solution with 0.1 M tetrabutylammoniumhexafluorophosphate (TBAPF₆) as the supporting electrolyte at scan rate100 mV/s unless otherwise stated. All electrochemical solutions werepurged with dry Ar for 15 minutes at least to deoxygenate the system.Under these conditions, a Fc/Fc⁺ standard was calibrated to be 0.40 V.In solution, monomer concentration was about ˜10⁻³ M.

Calculations: All calculations were performed using the Gaussian 03program. Optimized gas-phase structures were obtained using the densityfunctional theory (DFT) method B3LYP in conjunction with 6-31G(d,p)basis set, i.e., B3LYP/6-31G(d,p). California NanoSystems Institute atUCSB is acknowledged for computational resources.

FIG. 17 shows highest occupied molecular orbital (HOMO) and lowestunoccupied molecular orbital (LUMO) values measured electrochemicallyand calculated using the method above for example compounds 101, 103,104, 105, 106, 108.

Example 18 General Procedures for Fabrication of Devices

Device Fabrication: Indium tin oxide (ITO) substrates were prepared bywet cleaning and then UV/ozone treatment. A 50 nm hole injection layer(Plextronics Plexcore OC AQ-1300) was spin coated on top of an ITOsubstrate. A solution of filtered (1 μm Whatman PTFE filter) 103:PC₇₁BMwith varied ratios in chloroform was spin coating onto the ITO/PEDOT:PSSsubstrate at varied spin speeds for different thicknesses. The PC₇₁BMwas 99% pure and used as received from Solenne, and chloroform was usedas received from Sigma-Aldrich Inc. The 103:PC₇₁BM films thicknesseswere determined by profilometry. Devices had a 13 mm² area Al cathodeevaporated on top of the 103:PC₇₁BM film in a vacuum (˜10⁶ torr) at rateof 1 Å sec⁻¹ for 10 nm and then 2.5 Å sec¹ with a total thickness ofapproximately 100 nm. All fabrication and testing were carried outinside a nitrogen atmosphere drybox.

Device testing. Device J-V curves were measured with a Keithley 2602source-measure unit while illuminated with a simulated 100 mWcm⁻² AM 1.5G light source using a 300W Xe arc lamp with an AM1.5 global filter.Solar-simulator illumination intensity was measured using a standardsilicon photovoltaic with a protective KG1 filter calibrated by theNational Renewable Energy Laboratory. IPCE spectra measurements weremade with a 75W Xe source, monochromator, optical chopper, lock-inamplifier, and a National Institute of Standards and Technologytraceable silicon photodiode for monochromatic power-densitycalibration. Mismatch factors of the integrated IPCE for the deviceswere calculated to be less than 3.1%

Example 19

Organic Solar Cell Device using Compound 103

FIG. 18 shows the energy level diagram of a standard bulk-heterojunctionsolar cell device fabricated using compound 103.

Example 20

FIG. 19 and Table 1 show current-voltage plots of bulk heterojunctiondevices fabricated using the device architecturesITO/PEDOT:PSS/103:PC₇₁BM/Al. The active layer composition was variedfrom 30:70 103:PC₇₁BM to 70:30 103:PC₇₁BM. The active layers were castfrom 2% chloroform solutions at 1500 rpm, Active layer thickness=75 nm.

Example 21

FIG. 20 and Table 2 show the current-voltage plots of BHJ devicesfabricated using the device architectures ITO/PEDOT:PSS/103:PC₇₁BM/Al.Active layer composition was varied from 30:70 103:PC₇₁BM to 70:30103:PC₇₁BM. Active layers cast from 2% chloroform solutions at 1500 rpm.Active layer thickness=75 nm. Devices annealeds at 110° C. for 2 minutesunder N₂.

Example 22

FIG. 21 and Table 3 show current-voltage plots of bulk heterojunctiondevices fabricated using the device architecturesITO/PEDOT:PSS/103:PC₇₁BM/Al. The active layer composition was variedfrom 30:70 103:PC₇₁BM to 70:30 103:PC₇₁BM. The active layers were castfrom 2% chloroform solutions at 2500 rpm. Active layer thickness=85 nm.

Example 23

FIG. 22 and Table 4 show the current-voltage plots of BHJ devicesfabricated using the device architectures ITO/PEDOT:PSS/103:PC₇₁BM/Al.Active layer composition was varied from 30:70 103:PC₇₁BM to 70:30103:PC₇₁BM. Active layers cast from 2% chloroform solutions at 2500 rpm.Active layer thickness=85 nm. Devices annealed at 110° C. for 2 minutesunder N₂.

Example 24

FIG. 23 and Table 5 show current-voltage plots of bulk heterojunctiondevices fabricated using the device architecturesITO/PEDOT:PSS/103:PC₇₁BM/Al. The active layer composition was variedfrom 30:70 103:PC₇₁BM to 70:30 103:PC₇₁BM. The active layers were castfrom 2% chloroform solutions at 3500 rpm. Active layer thickness=105 nm.

Example 25

FIG. 24 and Table 6 show the current-voltage plots of BHJ devicesfabricated using the device architectures ITO/PEDOT:PSS/103:PC₇₁BM/Al.Active layer composition was varied from 30:70 103:PC₇₁BM to 70:30103:PC₇₁BM. Active layers cast from 2% chloroform solutions at 3500 rpm.Active layer thickness=105 nm. Devices annealed at 110° C. for 2 minutesunder N₂.

Example 26

FIG. 25 shows the best current-voltage plots of BHJ devices fabricatedusing the device architectures ITO/PEDOT:PSS/103:PC₇₁BM/Al. Active layercomposition was 60:40 103:PC₇₁BM. Active layers cast from 2% chloroformsolutions at 2500 rpm. Active layer thickness=85 nm. Device annealed at110° C. for 2 minutes under N₂.

Example 27

FIG. 26 shows the EQE spectra of best BHJ devices fabricated using thedevice architectures ITO/PEDOT:PSS/103:PC₇₁BM/Al. Active layercomposition was 60:40 103:PC₇₁BM. Active layers cast from 2% chloroformsolutions at 2500 rpm. Active layer thickness=85 nm. Device annealed at110° C. for 2 minutes under N₂.

Example 28

FIG. 27 shows the UV-vis-NIR absorption spectra of a 60:40 (w/w) blendof 103:PC₇₁BM as-cast film from CHCl₃ (solid), and annealed film 110° C.2 minutes (large dashed).

Example 29

Field Effect Transistor

FIG. 28 shows an example of an organic field effect transistor usingmaterial 103. Films were spun cast from 0.5% w/V in chloroform ontocleaned SiO₂ substrate at 2000 rpm for 40 s. An Au electrode wasthermally deposited at 4×10⁻⁷ Torr for 85 nm using a shadow mask withdimensions of L=40 μm and W=1 mm. For annealed samples, samples wereannealed on a hotplate at 120° C. for 15 minutes prior to electrodedeposition.

FIG. 28 shows the FET device output (top) and transfer (bottom)current-voltage curves

The average FET mobility of example compound 103 for as-castfilm=7.61×10⁻⁰³ cm²/Vs, while the average FET mobility of examplecompound 103 for annealed film=1.11×10⁻⁰³ cm²/Vs.

Example 30 Proposed Synthesis of Pyridaloxadiazole (PO) OrganicIntermediate

The pyridaloxadiazole (PO) core structure is synthesized as outlinedabove. For relevant literature see: M. Leclerc et al. Journal of theAmerican Chemical Society, 2008, 130, 732.; R A. J. Janssen et al.Chemistry of Materials, 2009, 21, 4669.; T. M. Swager et al.Macromolecules, 2008, 41, 5559.; March's Advanced Organic Chemistry,5^(th) Ed., Wiley, 2001.

The disclosures of all publications, patents, patent applications andpublished patent applications referred to herein by an identifyingcitation are hereby incorporated herein by reference in their entirety.

Although the foregoing invention has been described in some detail byway of illustration and example for purposes of clarity ofunderstanding, it is apparent to those skilled in the art that certainchanges and modifications will be practiced. Therefore, the descriptionand examples should not be construed as limiting the scope of theinvention.

What is claimed is:
 1. A compound of Formula IV-V:

where X₁ and Y₁ are selected from N and CH, where when X₁ is N, Y₁ isCH, and when X₁ is CH, Y₁ is N M is selected from sulfur (S), oxygen(O), or N-R₁, where R₁ is H, C₁-C₃₀ alkyl or C₆-C₃₀ aryl; K₁ isindependently selected from substituted or unsubstituted aryl orheteroaryl; each E₁ is independently either absent, or selected fromsubstituted or unsubstituted aryl or heteroaryl groups; each D₁ isindependently selected from substituted or unsubstituted aryl orheteroaryl groups; and each D₂ is independently selected from anonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstitutedaryl or heteroaryl group.
 2. A compound of claim 1 of Formula IVa orFormula IVb:

where M is selected from sulfur (S), oxygen (O), or N-R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where K₁ is independently selected fromsubstituted or unsubstituted aryl or heteroaryl groups; each D₁ isindependently selected from substituted or unsubstituted aryl orheteroaryl groups; and each D₂ is independently selected from anonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstitutedaryl or heteroaryl group.
 3. A compound of claim 1 of Formula Va orFormula Vb:

where M is selected from sulfur (S), oxygen (O), or N-R₁, where R₁ is H,C₁-C₃₀ alkyl or C₆-C₃₀ aryl; where K₁ is independently selected fromsubstituted or unsubstituted aryl or heteroaryl groups; each D₁ and E₁is independently selected from substituted or unsubstituted aryl orheteroaryl groups; and each D₂ is independently selected from anonentity, H, F, a C₁-C₁₆ alkyl group, or a substituted or unsubstitutedaryl or heteroaryl group.
 4. An electronic or optoelectronic devicecomprising a non-polymeric compound of claim 1, where said non-polymericcompound is an electron acceptor or is an electron donor in an activelayer of the electronic or optoelectronic device.
 5. An electronic oroptoelectronic device comprising a non-polymeric compound of claim 3,where said non-polymeric compound is an electron acceptor or is anelectron donor in an active layer of the electronic or optoelectronicdevice.
 6. A device comprising: 1) a first hole-collecting electrodeoptionally coated onto a transparent substrate; 2) an optional layer orlayers adjacent to the first electrode selected from anelectron-blocking layer, exciton-blocking layer, or hole-transportinglayer; 3) a layer comprising a mixture of an electron acceptor materialand an organic non-polymeric electron donor, said electron donorcomprising a compound of claim 1; 4) an optional layer or layersselected from a hole-blocking layer, exciton-blocking layer, orelectron-transporting layer; and 5) a second electron-collectingelectrode.
 7. A device comprising: 1) a first hole-collecting electrodeoptionally coated onto a transparent substrate; 2) an optional layer orlayers adjacent to the first electrode selected from anelectron-blocking layer, exciton-blocking layer, or hole-transportinglayer; 3) a layer comprising a mixture of an electron acceptor material,and an organic non-polymeric electron donor, said electron donorcomprising a compound of claim 3; 4) an optional layer or layersselected from a hole-blocking layer, exciton-blocking layer, orelectron-transporting layer; and 5) a second electron-collectingelectrode.
 8. A device comprising: 1) a first hole-collecting electrodeoptionally coated onto a transparent substrate; 2) an optional layer orlayers adjacent to the first electrode selected from anelectron-blocking layer, exciton-blocking layer, or hole-transportinglayer; 3) a layer comprising a mixture of an organic non-polymericelectron acceptor material and an electron donor, said electron acceptorcomprising a compound of claim 1; 4) an optional layer or layersselected from a hole-blocking layer, exciton-blocking layer, orelectron-transporting layer; and 5) a second electron-collectingelectrode.
 9. A device comprising: 1) a first hole-collecting electrodeoptionally coated onto a transparent substrate; 2) an optional layer orlayers adjacent to the first electrode selected from anelectron-blocking layer, exciton-blocking layer, or hole-transportinglayer; 3) a layer comprising a mixture of an organic non-polymericelectron acceptor material and an electron donor, said electron acceptorcomprising a compound of claim 3; 4) an optional layer or layersselected from a hole-blocking layer, exciton-blocking layer, orelectron-transporting layer; and 5) a second electron-collectingelectrode.
 10. A device comprising: 1) a dielectric substrate; 2) anoptional layer or layers adjacent the dielectric substrate, used tomodify the surface energy of the dielectric and/or to facilitatedeposition of the active layer; 3) an active layer comprising an organicnon-polymeric hole transporting material comprising a compound of claim1; and 4) a metal electrode to facilitate charge injection andcollection.
 11. A device comprising: 1) a dielectric substrate; 2) anoptional layer or layers adjacent the dielectric substrate, used tomodify the surface energy of the dielectric and/or to facilitatedeposition of the active layer; 3) an active layer comprising an organicnon-polymeric electron transporting material comprising a compound ofclaim 1; and 4) a metal electrode to facilitate charge injection andcollection.
 12. A device according to claim 10, wherein the dielectricsubstrate is Si/SiO₂.
 13. A device according to claim 4, wherein thenon-polymeric compound has a solubility of at least about 5 mg/mL in anorganic solvent.
 14. The device of claim 13, wherein the organic solventis selected from chloroform, toluene, chlorobenzene, methylenedichloride, tetrahydrofuran, and carbon disulfide.
 15. The compound ofclaim 1, wherein K₁ is independently selected from C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups.
 16. The compound of claim 1,wherein K₁ is independently selected from C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups.
 17. The compound of claim 1,wherein K₁ is independently selected from C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups.